Capsules with a high active ingredient content

ABSTRACT

The invention relates to (dried) capsules with a high active-ingredient or active-substance content, to the use of the capsules in cosmetic and/or pharmaceutical compositions and to the production of said capsules.

FIELD OF THE INVENTION

The invention concerns the field of (dried) capsules with a high activeingredient or active substance content, their use in cosmetic and/orpharmaceutical compositions, and the production of said capsules.

PRIOR ART

Encapsulations or enclosures of active ingredients, in particularflavoring agents or fragrances or cosmetic or pharmaceutically activeingredients, belong to prior art, and often provide the possibility ofstabilizing the encapsulated or enclosed material and protecting it fromreactions with the medium in order to obtain the effect of the activeingredient and slowly release it. There are various possibilities forencapsulation materials. A matrix material known to the person skilledin the art is alginate.

Alginates are linear polysaccharides whose monomeric building blocks areβ-D-mannuronate and α-L-guluronate. The β-D-mannuronate andα-L-guluronate radicals in the alginate are linked to one another via1,4-glycosidic bonds and form sequences with homopolymers and analternating structure. The degree of polymerization is between 100 and3000, which corresponds to a molar mass of 20,000 to 600,000 u. Thehomopolymer sequences are classified into two different categories:while the so-called “MM blocks” are composed of β-1,4-glycosidicallylinked D-mannuronate radicals, the “GG blocks” contain L-guluronateradicals having α-1,4-glycosidic bonds. In the third alginate blocktype, the sequence with the alternating structure and the D-mannuronateand L-guluronate radicals are alternately linked to one another viaβ-1,4 and α-1,4-glycosidic bonds. As a result, all four possible typesof glycosidic bonds are present in the alginate: diequatorial (MM),diaxial (GG), equatorial-axial (MG), and axial-equatorial (GM).

Methods for the production of calcium alginate particles have also longbelonged to prior art. The so-called drip feed method is often used inproduction. In this method, a solution of sodium alginate is addeddropwise via a hollow needle or cannula to a solution of a crosslinkingagent, e.g. a calcium salt solution (an “ionogenic crosslinker”). Inorder to prevent agglomeration, rotating or vibrating needles orcannulas can be used. Other divalent cations such as Sr2⁺,Ba2^(+, Pb)2⁺, Cu2⁺, Cd2⁺, Co2⁺, Ni2⁺, Zn2⁺, and Mn2⁺ are also suitableas ionogenic crosslinkers. However, their use is limited by theirtoxicity. The purely ionogenic crosslinking and the gelation of thealginate solution connected therewith chiefly result from replacement ofthe Na+ ions of the guluronate in the polymer by e.g. Ca2⁺. Theresulting special spatial arrangement of the guluronic acid sequencesaround the divalent Ca2⁺ ion is known in the literature as the “egg boxmodel” and is responsible for the structure of the resulting gelnetwork. This imparts strength to the forming particles (beads).Spherical particles of alginate produced by dropwise addition of analginate solution to a reservoir of an ionogenic crosslinker are widelyknown in the literature for encapsulation of a wide range of substances,e.g. yeast cells (T. Shiotani at. al., Eur. J. Appl. Microbial.Biotechnol. 13 (2), 1981), bacteria (H. Provost et. al., BiotechnologyLetters, 7(4), 247-252, 1985), as well as therapeutic agents (U.S. Pat.No. 485,471). For incorporation purposes, the material to beencapsulated is added to the alginate solution prior to contact with thecrosslinking medium.

DE 10026453 A1 discloses magnetic and non-magnetic spherical particlescomposed of a dimensionally stable alginate gel that is crosslinked bysalt bridges between the carboxyl groups of the alginate. The sphericalparticles can contain incorporated magnetic material, alginate with aD-mannuronate (M):L-guluronate (G) ratio of 0.1:1 to less than 1:1, oneor a plurality of cationic species, preferably a divalent or multivalentmetal cation, and one or a plurality of agents with favorableproperties.

The subject matter of EP 1110462 A2 (Nutrinova) is an encapsulatedbiologically active food ingredient composed of a core containing atleast one dietary fiber which is surrounded by a biologically activesubstance and a capsule-forming substance surrounding the core, whereinthe dietary fibers may be wheat fibers or pectin, the biologicallyactive substance may be a nutrient, and the capsule-forming substancemay be an emulsifier.

EP 1295538 A2 (Nutrinova) discloses dietary fiber capsules, the core ofwhich contains locust bean fiber and is enclosed on all sides by capsulematerials, with the capsule materials being selected from solubledietary fibers, which may be alginate, pectin, gum arabic, or modifiedfibers.

EP 1508591 A1 (Symrise) discloses gelatin-free seamless capsules with aliquid core and a solid shell surrounding this core, with the shellbeing composed of agar, hydrolyzed starch, water, and one or moreadditives.

EP 2099889 B1 also discloses alginate capsules (beads), but for use indetergents, comprising.

EP 2340805 A2 (Blume) discloses nanocapsules containing at least thefollowing components: a liquid lipid core and a continuous shellsurrounding the core composed of at least one hydrophobically modifiedpolysaccharide and at least one membrane-forming emulsifier.

EP 0766515 E1 concerns alginate capsules containing active ingredientswhich are released on a delayed basis. The alginate capsules have acomposition in which the weight ratio of alginate to polyacrylic acid is75:2 to 75:10 and the polyacrylic acid has a molecular weight of 10 to250 kDa.

A problem with the particles of prior art, particularly when a highcontent of flavoring agents or fragrances is to be achieved, is that thecapsules are microbially unstable in a wet state. Improved stability canbe achieved by drying the capsules. In the drying process, however, theactive ingredients encapsulated in the capsules, particularly when theseare flavoring agents or fragrances, are frequently pressed out andunintentionally released, causing the particles to shrink and a portionof the encapsulated active ingredients (flavoring agents or fragrances)to be lost before actual use.

The object of the present invention was therefore to provide stablecapsules containing active ingredients or substances which allowtargeted release of the encapsulated active ingredients or substances,for example during heating, baking, or frying or on exposure to strongshearing forces such as chewing or rubbing. The object of the presentinvention was thus to develop capsules that are not water-based and arewater-soluble, as most foods and cosmetic products contain water, withthe result that the required release on heating, consumption, orexposure to shearing forces is not achieved to an optimal extent or isachieved only in a very limited manner.

Another object of the present invention was to develop capsules thatallow a variable content as well as a high content of activeingredients, so that the capsules can be used over the widest possiblerange of applications, such as in the cosmetic and pharmaceuticalfields, particularly in the areas of oral care or dermatology. Theactive ingredients and substances in the capsules are to bewater-insoluble in this case as well, and are only to be released byrubbing or shearing, e.g. on brushing the teeth or rubbing on the skin.

DESCRIPTION OF THE INVENTION

Capsules, comprising

-   (a) at least one gelable substance,-   (b) at least one emulsifier,-   (c) at least one filler, and-   (d) at least one active ingredient an active substance of which is    to be encapsulated, with the active ingredient (d) being dispersed    in an emulsion comprising the gelable substance (a), the emulsifier    (b), and the filler (c), are the subject matter of the invention.

In a preferred embodiment, the gelable substance a) is selected from thegroup composed of alginate, pectin, agar-agar, carrageenan, gellan gum,gelatins, modified cellulose, and/or proteins, the emulsifier b) isselected from the group composed of polysorbates, sugar esters,saponins, gum arabic, and/or modified starch, and the filler c) isselected from the group composed of vegetable fibers, microcrystallinecellulose, silica gels, native starch and/or silicates.

Surprisingly, it was found that when the capsule matrix is composed ofan emulsion comprising at least one gelable substance, at least oneemulsifier, and at least one filler, active ingredients or activesubstances can be incorporated into the capsule matrix in finelydispersed form. This results in a high active ingredient or activesubstance content of the capsule matrix with the desired activeingredient or active substance and increased stability of the capsules,so that the active ingredients or active substances are not pressed outin the capsule drying phase and unintentionally released or destroyed.

Preferably, the capsules according to the invention have an extremelyhigh active ingredient content, which is variably adjusted according toapplication requirements. Accordingly, the capsules according to theinvention preferably have an active ingredient content of 20 to 95 wt %.The active ingredient or active substance content depends on the finalapplication of the capsules and therefore varies according to the fieldof use. For example, capsules containing flavoring agents or fragrancesshould preferably have a content of up to 95 wt %, while capsules usedin the field of medicine should preferably have a content oftherapeutically active ingredients of 20-60 wt %, and more preferably30-50 wt %. In the field of medicine, the content of the capsulesnaturally also depends on the dosage and the desired amount of theactive ingredient to be released. The capsules according to theinvention can thus be loaded accordingly. The content can becorrespondingly varied and adjusted depending on the applicationrequirements. Accordingly, the aforementioned content ranges are to beunderstood as possible example values and by no means limit theproducible content.

The use of the capsules according to the invention in toothpaste isparticularly advantageous, as the capsules according to the inventionhave a particularly favorable stabilizing effect on the encapsulatedsubstances in the toothpaste, allowing them to be released or deliveredin a controlled manner at the time of use (brushing of the teeth). Theencapsulated active ingredients or active substances are preferablycleaning agents, foaming agents, wetting and moisturizing agents, tasteand flavoring agents, and preservatives, as well as dyes and additives,and in medicinal toothpastes or dental creams, active ingredients forprophylaxis, particularly of parodontitis and caries (fluoride).Preferably, such a capsule for use in toothpaste has a content of theactive ingredients or active substances of 50 to 80 wt %, and inflavorings even up to 95 wt %.

The use of the capsules according to the invention in cosmetic products,in particular in the area of dermatology, such as (skin) creams, pastes,gels, and lotions, but also sprays, is also particularly advantageous,as the capsules according to the invention have the effect ofparticularly favorably stabilizing the desired substances, preferablyfragrance and flavoring agents or cosmetic active substances, and onlyreleasing them in a controlled manner at the time of use (by rubbingonto the skin). Preferably, in cosmetic products, such a capsule has acontent of the active ingredients or active substances of 40 to 80 wt %,and in fragrances and flavorings, even as much as 95 wt %.

Preferably, the capsules according to the invention can have an averagediameter of 200 to 1500 μm, preferably 400 to 900 μm, and particularlypreferably 500 to 800 μm. The capsule size can be varied and adjustedaccordingly depending on the application requirements. Accordingly, theaforementioned capsule size ranges are to be understood as possibleexample values and by no means limit the producible capsule sizes.

In the present application, the term capsule is used as a synonym forthe term particle. The two terms are to be understood as beingequivalent and mutually interchangeable.

In the present application, “gelable substances” are understood to becompounds which swell (up) in water or bind water, thus causing gelationand forming a gelatinous mass.

Suitable gelable substances that can be used according to the inventionare selected from the group composed of alginate, pectin, agar-agar,carrageenan, gellan gum, gelatins, modified cellulose, and/or proteins.

Particularly preferred are alginate, pectin, carrageenan and/or gellangum, and most particularly preferred are alginate and/or pectin and/orgellan gum, so that in a preferred embodiment, the gelable substance isalginate and/or pectin and/or gellan gum, and so that the resultingcapsules are alginate based and/or pectin based and/or gellan gum basedcapsules, preferably pectin or alginate or alginate-pectin oralginate-gellan gum based capsules.

Preferably, in a mixture of alginate and pectin or alginate and gellangum, the capsules according to the invention show a preferred ratio ofalginate to pectin of 1:2 to 2:1, and preferably a ratio of alginate togellan gum of 3:2 to 3:1.

Alginate is the general designation for alginic acid and its salts. TheM:G ratio of the alginate used in the present application is preferably0.1:1 to less than 1:1, for example 0.1:1 to 0.99:1. This means that inthe alginate used, the number of G radicals is greater than that of theM radicals. The M:G ratio is preferably 0.1:1 to 0.8:1, and particularlypreferably 0.2:1 to 0.8:1. Suitable algae genera for the production ofalginate include Laminaria, Ecklonia, Macrocystis, Lessonia,Ascophyllum, and Durvillea.

Sodium alginate (E 401), potassium alginate (E 402), ammonium alginate(E 403), calcium alginate (E 404), or propylene glycol alginate (PGA, E405) is preferably used as the alginate. Suitable alginates areavailable under the brand name “Manguel” (Manguel GMB) from the firmInternational Speciality Products, under the brand name “Protonal” fromthe firm FMC BioPolymer, and under the brand names “Satialgine”,“Cecalgum” and “Algogel” from the firm Texturant Systems.

The cationic species for forming a gel matrix with the alginate canbasically be any species that is capable of forming a gel matrix withthe alginate. Metal cations are preferred, particularly those which formdivalent or polyvalent metal salts in an aqueous solution.

According to the invention, therefore, in the case of an aqueoussolution of an alkali or ammonium salt of alginic acids or pectic acids,crosslinking agents are used that preferably contain a divalent cation,preferably calcium. According to the invention, when carrageenan isused, a crosslinking agent, preferably with potassium ions, is used.

Pectins are vegetable polysaccharides, more specifically polyuronides.The substance class of the pectins occurs in numerous structures. All ofthese structures have in common that they are polysaccharides whose maincomponent (to at least 65 wt %) is α-D-galacturonic acid (pKa value 2.9)as a monomer. These galacturonic acid monomers are bonded to one anothervia α-1,4-, and usually also to a minor extent via β-1,4-glycosidicbonds, and thus form the backbone of the pectin molecule. This linearbackbone is periodically interrupted by 1,2-bonds with α-L-rhamnose. Thesystematic name for pectin is therefore rhamnogalacturonic acid.

The incorporation of rhamnose units leads to disturbances in theformally linear polygalacturonic acid chain: the chains are “kinked”. Onthe other hand, the rhamnose structural elements in natural pectins bearoligomeric side chains composed of the sugars arabinose, galactose orxylose. In turn, these neutral sugar side chains can be classified intoarabinans, galactans, and arabinogalactan I, as well as arabinogalactanII, which is bonded to proteins, but is often also included among thehemicelluloses. The side chains usually consist of 1 to 50 sugar units.In industrial production of pectins, these side chains are largely lost,in particular the acid-labile arabinofuranose. The branched regions ofthe chain caused by L-rhamnose and its side chains do not occurregularly, but accumulate in the so-called “hairy regions”. In contrast,the linear parts of the chain are referred to as “smooth regions”.

In addition to this branching of the main chain, the pectinmacromolecule also has other characteristics. The hydroxy groups on theC₂ or C₃ atom of the galacturonic acid units are acetylated orsubstituted to a minor extent by further neutral sugars such asD-galactose, D-xylose, L-arabinose, or L-rhamnose—predominantly in thehairy regions in this case as well. The carboxy groups of thepolygalacturonic acid are often esterified with methanol. The degree ofesterification and acetylation fluctuates depending on the origin of thepectin, but is of decisive importance for the chemical properties.Pectins are therefore classified based on their average degree ofesterification VE.

Pectins are found in all higher land plants. In this case, pectins arefound in all of the more solid components, such as the stems, flowers,leaves, etc. Particularly rich in pectin are plant parts havingrelatively tough/hard components, e.g. citrus fruits or inflorescencesof sunflowers. The pectin content varies from plant to plant; forexample, apples contain approx. 1-1.5%, oranges approx. 0.9-3.5%, citruspeels (from oranges and lemons) approx. 30%, apricots approx. 1%,cherries approx. 0.4%, carrots approx. 1.4%, oranges approx. 0.5-3.5%,and quinces approx. 0.5% pectin.

Suitable pectins for the present invention are apple, citrus, andgrapefruit pectins, which are available for example from the firmHerbstreith & Fox.

Suitable gelable substances that are modified cellulose are preferablyselected from methyl cellulose (MC), hydroxyethyl cellulose (HEC) andcarboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), andhydroxypropyl cellulose (HPC) and ethyl hydroxyethyl cellulose (EHEC).

Suitable gelable substances that are starch (derivatives) are preferablyselected from e.g. hydroxyethyl starch and hydroxypropyl starch.

The gelable substance, which is preferably alginate and/or pectin and/orgellan gum, is preferably used in an amount of 0.5 to 3 wt % withreference to the total weight of a capsule. Preferably, the gelablesubstance is used in an amount of 0.7 to 2.0 wt %, particularlypreferably in an amount of 1.0 to 1.7 wt %, and most preferably in anamount of 1.1 to 1.5 wt % on a dry matter basis with respect to thetotal weight of a capsule.

Suitable emulsifiers according to the invention are selected from thegroup composed of polysorbates, sugar esters, saponins, gum arabic,modified gum arabic, and/or modified starch.

Preferably, the following polysorbates are used:

polysorbate 20 (polyoxyethylene (20) sorbitan monolaurate) (E 432)

polysorbate 21 (polyoxyethylene (4) sorbitan monolaurate)

polysorbate 40 (polyoxyethylene (20) sorbitan monopalmitate) (E 434)

polysorbate 60 (polyoxyethylene (20) sorbitan monostearate) (E 435)

polysorbate 61 (polyoxyethylene (4) sorbitan monostearate)

polysorbate 65 (polyoxyethylene (20) sorbitan tristearate) (E 436)

polysorbate 80 (polyoxyethylene (20) sorbitan monooleate) (E 433)

polysorbate 81 (polyoxyethylene (5) sorbitan monooleate)

polysorbate 85 (polyoxyethylene (20) sorbitan trioleate) (Span 85)

polysorbate 120 (polyoxyethylene (20) sorbitan monoisostearate).

In a preferred embodiment, the emulsifiers are selected from the groupcomposed of gum arabic, modified gum arabic, and/or modified starch.

Suitable fillers according to the invention are selected from the groupcomposed of vegetable fibers, microcrystalline cellulose, silica gels,native starch, and/or silicates. Fiber plants are preferably used asfillers.

Accordingly, in a preferred embodiment of the invention, the filler usedis a vegetable fiber selected from apple fibers, bamboo fibers, oatfibers, pea fibers, potato fibers, and/or wheat fibers. Suitable fibersare available for example from the firm JELUCEL under the brand namesJELUCEL® WF, JELUCEL® BF, JELUCEL® OF, or also in the Vitacel® productline of the firm JRS. Particularly preferred in this case are applefibers, bamboo fibers, oat fibers, and/or wheat fibers.

The filler is preferably used in an amount of 0.5 to 5 wt % relative tothe total weight of the capsule. More preferably, the filler is used inan amount of 0.7 to 3.5 wt %, and even more preferably in an amount of0.8 to 1.5 wt % relative to the total weight of a capsule.

A particular challenge of the present invention was drying of thehigh-content capsules. It was important to produce capsules in which theactive ingredient, which is enclosed in matrix, is not pressed out bydrying, causing it to be released or destroyed prior to use.

A particular advantage of the capsules according to the invention isthat they can be easily dried without causing a major loss of theenclosed active ingredients and active substances (due to uncontrolledrelease). Therefore, the capsules according to the invention shouldpreferably have an AW value of less than or equal to 0.8, preferablyless than or equal to 0.7, and particularly preferably less than orequal to 0.6. The AW value is the measure of unbound and loosely boundwater, i.e. of the availability of water in food products or foodstuffsand preparations. ¹The AW value is therefore an important parameter forthe shelf life of foods. The higher the AW value, i.e. the more unboundwater a food contains, the more readily it can spoil. The reason is thatthe freely available water is of decisive importance mainly for thegrowth or metabolism of microorganisms. It is also required by someenzymes, the so-called hydrolases, for hydrolysis, i.e. for the cleavageof chemical bonds by a reaction with water. ¹¹http://www.1ebensmttellexikon.de/a0000420.php

For successful drying of the capsules, the combination according to theinvention of emulsifiers, preferably emulsifiers suitable forfoodstuffs, and fillers is of decisive importance.

A ratio of the emulsifier to the filler is preferably in the range of2.1:1.2, and particularly preferably in the range of 1:1.

The use of the aforementioned fillers has the particular advantage ofincreasing the dry matter in the capsule and binding the activeingredient or the active substance encapsulated in the matrix, providingstability during drying. For this reason, the filler is an essentialcomponent of the present invention.

Depending on the requirements of the final application, the capsuleproperties can be controlled by the selection and amount of theemulsifier and the filler, thus affecting properties such as the releasebehavior of the active ingredient and the stability of the capsule andits contents.

A further advantage of the capsules according to the invention is theirstability, which makes it possible to use said capsules in a widevariety of different applications, in order to bring the desired activeingredients and active substances according to the applicationrequirements into the corresponding medium and release them in acontrolled manner as needed.

Accordingly, a further preferred embodiment of the present inventioncomprises capsules containing active ingredients or active substancesselected from the group composed of flavorings, fragrances, dietarysupplements such as vitamins, minerals, antioxidants, anthocyanins,coenzyme 10, etc., as well as cosmetic active substances and/orpharmaceutically active substances.

Moreover, a preferred embodiment of the invention is use of the capsulesaccording to the invention in cosmetic products, pharmaceutical agents,or foods and beverages.

Further subject matter of the invention is the production of thecapsules according to the invention.

The method for production of the capsules according to the inventioncomprises

-   (i) formation of a mixture of    -   (a) at least one gelable substance,    -   (b) at least one emulsifier,    -   (c) at least one filler, and    -   (d) at least one active ingredient or an active substance,-   (ii) addition of drops of the mixture of i) to a solution of a    multivalent cation, so that crosslinking occurs and gelation takes    place,-   (iii) separation of the capsules formed from step ii), and-   (iv) drying of the capsules obtained from step iii).

The subject matter of the invention further includes capsules which canbe obtained by means of the steps, comprising:

-   (i) formation of a mixture of a) at least one gelable substance, b)    at least one emulsifier, c) at least one filler, and d) at least one    active ingredient or active substance,-   (ii) addition of drops of the mixture of i) to a solution of a    multivalent cation, so that crosslinking occurs and gelation takes    place,-   (iii) separation of the capsules formed from step ii), and-   (iv) drying of the capsules obtained from step iv), wherein the    gelable substance a) is selected from the group composed of    alginate, pectin, agar-agar, carrageenan, gellan gum, gelatins,    modified cellulose, and/or proteins, the emulsifier b) is selected    from the group composed of polysorbates, sugar esters, saponins, gum    arabic, and/or modified starch, and c) the filler is selected from    the group composed of vegetable fibers, microcrystalline cellulose,    silica gels, native starch, and/or silicates.

According to the invention, an emulsion of a) at least one gelablesubstance, b) at least one emulsifier, c) at least one filler, and d) atleast one active ingredient or an active substance is produced. Discretedroplets are than produced from the emulsion, and these are placed in acell bath of multivalent cations, with the result that dimensionallystable, essentially water-insoluble capsules are produced.Advantageously, an alcohol-based solution, which preferably containscalcium ions, should be used.

In producing the droplets, the particle size can be adjusted by means ofthe dimensions of the needles/cannulas used. The use of rotating orvibrating needles/cannulas is also advantageous, as this allows morefavorable shearing off of the droplets. The use of a mobileprecipitation bath is also advantageous, so that the drops formed can betransported further and cannot agglomerate in one place.

The capsules obtainable in this manner can be rinsed with water toremove salt residues.

Drying of the capsules is carried out by fluidized bed drying, in whichthe capsules to be dried are preferably placed in a stream of warm aircoming from below and thus suspended, mixed, and dried.

Preferably, the wet material is turbulently mixed in a hot stream of gasdirected upward and can thus dry with high heat and material transfercoefficients. The required gas flow rate preferably depends essentiallyon the particle size and density. The use of a perforated floor (holesheet, Conidur sheet, floors of fabric or sintered material) canpreferably prevent the solid material from falling through into the hotgas chamber. Heat is preferably supplied either by the drying gas oradditional heat exchangers (tube bundles or plates) can preferably beadded to the fluidized bed.

The fluidized bed dryers used for drying can be operated eithercontinuously or batch-wise. In continuous operation, the residence timein the dryer is preferably several minutes to hours; the unit istherefore also suitable for long-term drying. If a narrow residence timedistribution is required, a cascade fluidized bed can be used,preferably by means of separator plates, or the product flow can be madeto approximate a perfect piston flow using meandering installations. Inparticular, larger dryers are preferably subdivided into several dryingzones, which are operated with different gas flow rates andtemperatures. The last zone can then be used as a cooling zone. In thefeeding area of the wet material, particular care should be taken toensure that no clumping occurs. There are various possible ways ofaccomplishing this, e.g. using a locally higher gas flow rate or anagitator.

In such a method, alginate and/or pectin and/or gellan gum basedcapsules are preferably produced. The capsules according to theinvention are preferably water insoluble and stable. The wall materialof the capsules according to the invention is composed of a matrix ofwater-insoluble, multivalent cations, preferably calcium ions, and afiller, and the active ingredients or active substances are preferablyembedded in the matrix. The capsules according to the inventionpreferably do not show a typical core-shell structure in which theactive ingredient or the active substance is enclosed in core andsurrounded by a shell.

Rather, the active ingredients or active substances should be embeddedin the capsule matrix is a dispersed manner.

In a preferred embodiment, the capsules according to the invention areparticularly suitable for use in cosmetic products, pharmaceuticalagents, or foods and beverages.

Moreover, further subject matter of the present invention is the use ofthe capsules according to the invention for the production of cosmeticproducts, pharmaceutical agents, or foods and beverages.

Moreover, further subject matter of the present invention is the use ofthe capsules according to the invention for the production ofpharmaceutical agents or cosmetic products for use on the skin or oraluse.

In particular, the capsules according to the invention are suitable forenclosing the active ingredient and active substances in the matrix sothat these can later be released in a controlled manner. Accordingly, ina preferred embodiment, the capsules according to the invention are usedfor the controlled, prolonged, and delayed delivery or release of activeingredients and active substances.

Preferably, the capsules according to the invention are used for theproduction of pharmaceutical agents or cosmetic products, which areparticularly suitable for use on the skin. Preferred in this case areboth cosmetic products and pharmaceutical agents in the form ofointments, creams, lotions, gels and pastes, and sprays.

Preferably, an ointment, cream, lotion, gel, and paste is understood tobe a semisolid spreadable preparation which is suitable for applicationto the skin.

Such preparations, for example, may be based on an aqueous (hydrophilic)and an oily or fatty (lipophilic) component, with one component beingdistributed in the other in the form of an emulsion.

Hydrophilic creams of the O/W type or lipophilic creams of the W/O typemay also be used. There are also creams that cannot be clearlyclassified as either the O/W or the W/O type which consist of gel-likelipophilic and hydrophilic phases that are coherently distributed in oneanother (amphiphilic cream). Multiple emulsion structures of the W/O/Wemulsion type are also possible. In this case, however, the inner phaseis in the form of an emulsion. Tiny water droplets are also embedded inthe inner oil phase. This emulsion type is intended to combine theadvantages of both W/O and O/W emulsions.

Further preparations are preferably ointments, as a rule in the form ofa semisolid and homogenous appearing preparation that is suitable foruse on the skin (e.g. as a wound ointment) or the mucous membranes.Ointments are usually used for local application of the activeingredient or for the care and protection of the skin or mucousmembranes. Preferably, an ointment is composed of a hydrophobic orhydrophilic base of natural or synthetic substances and can be asingle-phase (e.g. Vaseline) or multi-phase (e.g. water-in-oil) system.

A further preferred preparation is the gel. Gels can be described asviscoelastic fluids. Their fluid properties thus lie between those of anideal liquid and those of an ideal solid. A gel is a finely-dispersedsystem of at least one solid and one liquid phase. The solid phase formsa sponge-like three-dimensional network whose pores are filled with aliquid (lyogel) or a gas (xerogel). If the network is highly porous andthe incorporated gas is air, the gel is referred to as an aerogel. Inthis case, the two phases interfuse completely (bicoherence).

Preferably, preparations are also in the form of pastes. A paste issolid-liquid mixture (suspension) with a high content of solids. Pastesare preferably no longer flowable, but can be spread. For example, apaste is an ointment-powder mixture, and in particular a semisoliddosage form with a high content of dispersed solids (a “suspensionointment” with a solid content of 30 wt %example of such a paste isPasta Zinci (zinc ointment)).

An example in which a product may be in a variety of preparation formsis that of toothpaste (or dental cream or gel), which can be used inboth the medical and cosmetic fields, and thus constitutes a broadproduct range. The main components are cleaning agents, foaming agents,wetting and moisturizing agents, taste and flavoring agents, andpreservatives, as well as dyes and additives. Moreover, toothpastes alsocontain active ingredients for dental prophylaxis, particularly ofparodontitis and caries (fluoride).

The capsules according to the invention allow active ingredients andactive ingredient substances to be incorporated in a particularlyfavorable manner into the above-described preparations (ointments,creams, lotions, gels and pastes), as the capsules are water-insolubleand therefore stable in the base preparation and are not destroyed,allowing the active ingredients or active substances to be released ordelivered only at the time of use, preferably by mechanical shearingforces such as rubbing onto the skin or brushing of the teeth.

The capsules according to the invention are suitable in particular foruse or incorporation in the aqueous/water-based medium, as the capsulesare softened and caused to swell slightly by the surrounding water. Thisphenomenon allows the capsules, during use in particular in ointments,creams, lotions, gels and pastes, to show very favorable properties inrubbing and spreading onto the skin, thus making it possible to releasethe active ingredients and active substances in a controlled manner.

It is also possible to use the capsules according to the invention infoods and beverages. Here, the focus is on special foods and beveragesfor which specified substances are to be encapsulated and then laterreleased at the time of use.

The foods and beverages are preferably spreadable food products such asbread spreads, meat paste, but also baked goods such as bread, drybiscuits, cakes, waffles and other pastries, sweets (such as chocolates,chocolate bar products, other products in bar form, fruit gums, hard andsoft caramels, chewing gum), snack articles (such as baked or friedpotato chips or potato dough products, maize or peanut-basedextrudates), fat- and oil-based products or emulsions thereof (such asmargarine, mayonnaise, remoulade, dressings), milk products (such asyoghurt, creams, spreads), and delicatessen products such as chickensalads.

Particularly preferred here are snacks, baked goods, margarine, spreads,and sweets such as chewing gums and fruit gums.

Preferably, in use in foods and beverages, flavoring agents areencapsulated in the capsules according to the invention in order toachieve a so-called “flavor burst effect” on consumption. For example,fruit flavoring agents such as orange, strawberry, apple flavors, etc.can be encapsulated in the capsules according to the invention, andthese capsules can then for example be incorporated into chicken salad,chocolate, or ice cream, producing a surprising effect when these foodsare chewed. A particular taste experience is also provided if, forexample, the flavor-containing capsules according to the invention arebaked into frozen waffles, cookies, or the like, so that a surprisingflavor effect can be achieved on consumption.

Chewing Gums

The preferred oral preparations can also be chewing gums. These productstypically comprise a water-insoluble and a water-soluble component.

The water-insoluble base, which is also referred to as the “gum base”,ordinarily comprises natural or synthetic elastomers, resins, fats andoils, plasticizers, fillers, dyes and optionally waxes. The amount ofbase in the total composition is ordinarily 5 to 95, preferably 10 to50, and in particular 20 to 35 wt %. In a typical embodiment of theinvention, the base is composed of 20 to 60 wt % synthetic elastomers, 0to 30 wt % natural elastomers, 5 to 55 wt % plasticizers, 4 to 35 wt %fillers and, in subordinate amounts, additives such as dyes,antioxidants and the like, with the proviso that they are water-solubleat most in small amounts.

Suitable synthetic elastomers are, for example, polyisobutylenes havingaverage molecular weights (according to GPC) of 10,000 to 100,000 andpreferably 50,000 to 80,000, isobutylene-isoprene copolymers (“butylelastomers”), styrene-butadiene copolymers (styrene:butadiene ratio e.g.from 1:3 to 3:1), polyvinyl acetates having average molecular weights(according to GPC) of 2000 to 90,000 and preferably 10,000 to 65,000,polyisoprenes, polyethylene, vinyl acetate-vinyl laurate copolymers, andmixtures thereof. Examples of suitable natural elastomers are rubberssuch as smoked or liquid latex or guayule, as well as natural rubberssuch as jelutong, lechi caspi, perillo, sorva, massaranduba balata,massaranduba chocolate, nispero, rosindinba, chicle, gutta hang kang,and mixtures thereof. The choice of synthetic and natural elastomers andthe mixing ratios thereof is essentially determined by whether bubblesare to be produced with the chewing gums (bubble gums) or not. Elastomermixtures comprising jelutong, chicle, sorva, and massaranduba arepreferably used.

In most cases, the elastomers are found to be too hard or to haveinsufficient deformability in processing, so that it has been found tobe advantageous to use special plasticizers together with them, which ofcourse must also meet in particular all the requirements for approval asfood additives. In this respect, primarily suitable compounds are estersof resin acids, for example esters of lower aliphatic alcohols orpolyols with wholly or partially hardened, monomeric or oligomeric resinacids. In particular, methyl, glycerol, or pentaerythritol esters andmixtures thereof are used for this purpose. Alternatively, terpeneresins, which can be derived from α-pinene, β-pinene, δ-limonene, ormixtures thereof, can also be used.

Suitable examples of fillers or texturizing agents include magnesium orcalcium carbonate, ground pumice, silicates, particularly magnesium oraluminum silicates, clays, aluminum oxides, talcum, titanium dioxide,and mono-, di-, and tricalcium phosphate, as well as cellulose polymers.

Suitable emulsifiers are tallow, hardened tallow, hardened or partiallyhardened vegetable oils, cocoa butter, partial glycerides, lecithin,triacetin, and saturated or unsaturated fatty acids with 6 to 22 andpreferably 12 to 18 carbon atoms, and mixtures thereof.

Examples of suitable dyes and whitening agents include the FD and Ctypes approved for the coloring of foods, plant and fruit extracts, aswell as titanium dioxide.

The basic materials can contain waxes or be wax-free; examples ofwax-free compositions can be found inter alia in patent specificationU.S. Pat. No. 5,286,500, the contents of which are hereby expresslyincorporated by reference.

In addition to the water-insoluble gum base, chewing gum preparationsregularly contain a water-soluble component, composed for example ofsofteners, sweeteners, fillers, flavorings, flavor enhancers,emulsifiers, dyes, acidifiers, antioxidants, and the like, provided inthis case that the components have at least sufficient water solubility.Depending on the water solubility of the special components, therefore,the individual components can belong both to the water-insoluble and thewater-soluble phase. However, it is also possible to use combinations,for example of a water-soluble and a water-insoluble emulsifier, withthe individual components being in different phases. Ordinarily, thewater-insoluble component accounts for 5 to 95%, and preferably 20 to 80wt % of the preparation.

Water-soluble softeners or plasticizers are added to the chewing gumcompositions in order to improve chewability and chewing feel, and aretypically contained in the mixtures in amounts of 0.5 to 15 wt %.Typical examples are glycerol, lecithin, aqueous solutions of sorbitol,hydrogenated starch hydrolysates, and corn syrup.

Both sugar-containing and sugar-free compounds are suitable assweeteners and are used in amounts of 5 to 95, preferably 20 to 80, andin particular 30 to 60 wt % relative to the chewing gum composition.Typical saccharide sweeteners are sucrose, dextrose, maltose, dextrin,dried invert sugar, fructose, levulose, galactose, corn syrup, andmixtures thereof. Suitable sugar substitutes include sorbitol, mannitol,xylitol, hydrogenated starch hydrolysate, maltitol and mixtures thereof.Other suitable additives include so-called HIAS (high intensityartificial sweeteners) such as sucralose, Aspartame, acesulfame salts,Alitame, saccharin and saccharin salts, cyclamic acid and salts thereof,glycyrrhizin, dihydrochalcone, thaumatin, monellin and the like,individually or in mixtures. Particularly effective compounds alsoinclude the hydrophobic HIAS, the subject matter of International PatentApplication WO 2002 091849 A1 (Wrigley's) as well as Stevia extracts andtheir active components, in particular ribeaudioside A. The amount ofthese substances used depends chiefly on their performance capacity andis typically in the range of 0.02 to 8 wt %.

Suitable fillers for the production of low-calorie chewing gums inparticular include polydextrose, Raftilose, Rafitiline,fructooligosaccharides (NutraFlora), palatinose oligosaccharides, guargum hydrolysates (Sun Fiber), and dextrins.

The choice of further flavorings is virtually unlimited and is not ofcritical importance for the nature of the invention. The total amount ofall flavorings is ordinarily 0.1 to 15 wt % and preferably 0.2 to 5 wt %relative to the chewing gum composition. Suitable further flavoringsare, for example, essential oils, synthetic flavors and the like, suchas aniseed oil, star anise oil, cumin oil, eucalyptus oil, fennel oil,lemon oil, wintergreen oil, clove oil and the like, as are also used,for example, in oral and dental care compositions.

The chewing gums can further comprise further auxiliary substances andadditives which are suitable, for example, for tooth care, especiallyfor controlling plague and gingivitis, such as chlorhexidine, CPC, ortriclosan. pH regulators (e.g. buffers or urea), active ingredientsagainst caries (e.g. phosphates or fluorides), and biogenic activeingredients (antibodies, enzymes, caffeine, plant extracts) can furtherbe present, provided that these substances are approved for foodstuffsand do not interact with one another in an undesirable manner.

Cosmetic and/or Pharmaceutical Agents

The capsules according to the invention are particularly suitable forincorporating active ingredients and substances into cosmetic productsand/or pharmaceutical agents.

Preferably, therapeutically active ingredients can be encapsulated inthe capsules according to the invention. Cosmetic products andpharmaceutical agents preferably comprise a number of auxiliarysubstances and additives. As needed, these auxiliary substances andadditives can also be encapsulated in the capsules according to theinvention. Examples of typical auxiliary substances and additives thatcan be contained in cosmetic products and/or pharmaceutical agents andcan also be encapsulated in the capsules according to the inventioninclude mild surfactants, oil components, emulsifiers, pearlescentwaxes, cooling agents, bodying agents, thickeners, superfatting agents,stabilizers, polymers, silicone compounds, fats, waxes, lecithins,phospholipids, UV protection factors, humectants, biogenic activeingredients, antioxidants, deodorants, antiperspirants, antidandruffagents, film-forming agents, swelling agents, insect repellents,self-tanning agents, tyrosine inhibitors (depigmenting agents),hydrotropes, solubilizers, preservatives, perfume oils, dyes and thelike.

In particular, active ingredients such a cooling active ingredients aresuitable for being encapsulated in the capsules according to theinvention. In such encapsulation, it is preferable to carry out cooling,e.g. in creams, pastes, sprays etc. only at the time of use, i.e. onrubbing onto the skin. The capsules according to the invention areparticularly suitable for such use, e.g. as after-sun cream or after-sunsprays.

Surfactants

As surface-active substances, anionic, nonionic, cationic and/oramphoteric or zwitterionic surfactants whose content of the agents isordinarily approximately 1 to 70, preferably 5 to 50, and in particular10 to 30 wt % may be included. Typical examples of anionic surfactantsare soaps, alkyl benzene sulfonates, alkane sulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methylester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ethersulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide(ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylicacids and the salts thereof, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, N-acylamino acids such as acyllactylates, acyl tartrates, acyl glutamates, and acyl aspartates, alkyloligoglucoside sulfates, protein fatty acid condensation products (inparticular wheat-based plant products) and alkyl (ether) phosphates. Ifthe anionic surfactants contain polyglycol ether chains, these mayexhibit a conventional, but preferably a narrowed homolog distribution.Typical examples of nonionic surfactants are fatty alcohol polyglycolethers, alkyl phenol polyglycol ethers, fatty acid polyglycol esters,fatty acid amide polyglycol ethers, fatty amine polyglycol ethers,alkoxylated triglycerides, mixed ethers or mixed formals, optionallypartially oxidized alk(en)yl oligoglycosides or glucuronic acidderivatives, fatty acid N-alkyl glucamides, protein hydrolysates (inparticular wheat-based plant products), polyol fatty acid esters, sugaresters, sorbitan esters, polysorbates and amine oxides. If the nonionicsurfactants contain polyglycol ether chains, these may exhibit aconventional, but preferably a narrowed homolog distribution. Typicalexamples of cationic surfactants are quaternary ammonium compounds suchas dimethyl distearylammonium chloride, and esterquats, in particularquaternized fatty acid trialkanolamine ester salts. Typical examples ofamphoteric or zwitterionic surfactants are alkyl betaines,alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines. The above-mentioned surfactants areexclusively known compounds. Typical examples of particularly suitablemild surfactants, i.e. particularly gentle to the skin, are fattyalcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/ordialkyl sulfosuccinates, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acidglucamides, alkyl amidobetaines, amphoacetals and/or protein fatty acidcondensates, the latter preferably based on wheat proteins.

Oil Components

Examples of suitable oil components include

Guerbet alcohols based on fatty alcohols with 6 to 18, and preferably 8to 10 carbon atoms, esters of linear C₆-C₂₂ fatty acids with linear orbranched C₆-C₂₂ fatty alcohols or esters of branched C₆-C₁₃ carboxylicacids with linear or branched C₆-C₂₂ fatty alcohols, such as myristylmyristate, myristyl palmitate, myristyl stearate, myristyl isostearate,myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate,cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetylbehenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearylstearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearylerucate, isostearyl myristate, isostearyl palmitate, isostearylstearate, isostearyl isostearate, isostearyl oleate, isostearylbehenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleylstearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleylerucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenylisostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucylmyristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyloleate, erucyl behenate and erucyl erucate. Also suitable are esters oflinear C₆-C₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C₁₉-C₃₈ alkyl hydroxycarboxylic acids with linear orbranched C₆-C₂₂ fatty alcohols, in particular dioctyl malate, esters oflinear and/or branched fatty acids with multivalent alcohols (such aspropylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols,triglycerides based on C₆-C₁₀ fatty acids, liquid mono/di/triglyceridemixtures based on C₆-C₁₈ fatty acids, esters of C₆-C₂₂ fatty alcoholsand/or Guerbet alcohols with aromatic carboxylic acids, in particularbenzoic acid, esters of C₂-C₁₂ dicarboxylic acids with linear orbranched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branchedprimary alcohols, substituted cyclohexanes, linear and branched C₆-C₂₂fatty alcohol carbonates such as dicaprylyl carbonate (Cetiol® CC),Guerbet carbonates based on fatty alcohols with 6 to 18, and preferably8 to 10 carbon atoms, esters of benzoic acid with linear and/or branchedC₆-C₂₂ alcohols (e.g. Finsolv® TN), linear or branched, symmetrical orasymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl groupsuch as dicaprylyl ether (Cetiol® OE), ring-opening products ofepoxidized fatty acid esters with polyols, silicone oils(cyclomethicones, silicone methicone types, etc.) and/or aliphatic ornaphthenic hydrocarbons such as squalane, squalene, or dialkylcyclohexane.

Emulsifiers

Emulsifiers which may be used are for example nonionogenic surfactantsfrom at least one of the following groups:

-   -   addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5        mol of propylene oxide onto linear fatty alcohols with 8 to 22        carbon atoms, fatty acids with 12 to 22 carbon atoms, alkyl        phenols with 8 to 15 carbon atoms in the alkyl group, as well as        alkylamine with 8 to 22 carbon atoms in the alkyl radical;    -   alkyl and/or alkenyl oligoglycosides with 8 to 22 carbon atoms        in the alk(en)yl radical and ethoxylated analogs thereof;    -   addition products of 1 to 15 mol of ethylene oxide onto castor        oil and/or hardened castor oil;    -   addition products of 15 to 60 mol of ethylene oxide onto castor        oil and/or hardened castor oil;    -   partial esters of glycerol and/or sorbitan with unsaturated,        linear or saturated, branched fatty acids with 12 to 22 carbon        atoms and/or hydroxycarboxylic acids with 3 to 18 carbon atoms        as well as adducts thereof with 1 to 30 mol of ethylene oxide;    -   partial esters of polyglycerol (average intrinsic degree of        condensation 2 to 8), polyethylene glycol (molecular weight 400        to 5000), trimethylolpropane, pentaerythritol, sugar alcohols        (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl        glucoside, lauryl glucoside), and polyglucosides (e.g.        cellulose) with saturated and/or unsaturated, linear or branched        fatty acids with 12 to 22 carbon atoms and/or hydroxycarboxylic        acids with 3 to 18 carbon atoms, as well as adducts thereof with        1 to 30 mol of ethylene oxide;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol and/or mixed esters of fatty acids with 6 to 22        carbon atoms, methyl glucose and polyols, preferably glycerol or        polyglycerol;    -   mono-, di- and trialkyl phosphates as well as mono-, di- and/or        tri-PEG alkyl phosphates and salts thereof;    -   wool wax alcohols;    -   polysiloxane/polyalkyl/polyether copolymers or corresponding        derivatives;    -   block copolymers, e.g. polyethylene glycol-30        dipolyhydroxystearate;    -   polymer emulsifiers, e.g. Pemulen grades (TR-1,TR-2) from        Goodrich or Cosmediag SP from Cognis;    -   polyalkylene glycols, and    -   glycerol carbonate.

In the following, particularly suitable emulsifiers are discussed infurther detail:

Alkoxylates. The addition products of ethylene oxide and/or propyleneoxide onto fatty alcohols, fatty acids, alkyl phenols or castor oil areknown, commercially available products. These are homologous mixtureswhose average degree of alkoxylation corresponds to the ratio of theamounts ethylene oxide and/or propylene oxide and substrates with whichthe addition reaction is carried out. C_(12/18) fatty acid mono- anddiesters of addition products of ethylene oxide to glycerol are known asrefatting agents for cosmetic preparations.

Alkyl and/or alkenyl oligoglycosides. Alkyl and/or alkenyloligoglycosides, their production, and their use are known from priorart. They are produced in particular by reacting glucose oroligosaccharides with primary alcohols with 8 to 18 carbon atoms. Withrespect to the glycoside radical, both monoglycosides, in which a cyclicsugar radical is glycosidically bonded to the fatty alcohol, andoligomeric glycosides with a preferred degree of oligomerization ofapproximately 8 are suitable. Here, the degree of oligomerization is astatistical average value upon which a homolog distribution common forsuch technical products is based.

Partial glycerides. Typical examples of suitable partial glycerides arehydroxystearic acid monoglyceride, hydroxystearic acid diglyceride,isostearic acid monoglyceride, isostearic acid diglyceride, oleic acidmonoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride,ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic aciddiglyceride, linolenic acid monoglyceride, linolenic acid diglyceride,erucic acid monoglyceride, erucic acid diglyceride, tartaric acidmonoglyceride, tartaric acid diglyceride, citric acid monoglyceride,citric acid diglyceride, malic acid monoglyceride, malic aciddiglyceride, as well as technical mixtures thereof, which can containminor subordinate amounts of triglycerides from the production process.Addition products of 1 to 30, and preferably 5 to 10 mol of ethyleneoxide onto the aforementioned partial glycerides are also suitable.

Sorbitan esters. Examples of suitable sorbitan esters include sorbitanmonoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate,sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate,sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitansesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitanmonoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate,sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitansesquihydroxystearate, sorbitan dihydroxystearate, sorbitantrihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate,sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate,sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate,sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate,sorbitan trimaleate, as well as technical mixtures thereof. Additionproducts of 1 to 30, and preferably 5 to 10 mol of ethylene oxide ontothe aforementioned sorbitan esters are also suitable.

Polyglycerol esters. Typical examples of suitable polyglycerol estersare polyglyceryl-2-dipolyhydroxystearate (Dehymuls® PGPH),polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate(Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3diisostearate (Isolan® PDI), polyglyceryl-3 methyl glucose distearate(Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4caprate (polyglycerol caprate T2010/90), polyglyceryl-3 cetyl ether(Chimexane® NL), polyglyceryl-3 distearate (Cremophor® GS 32) andpolyglyceryl polyricinoleate (Admul® WOL 1403) polyglyceryl dimerateisostearate, and mixtures thereof. Examples of further suitable polyolesters, optionally reacted with 1 to 30 mol of ethylene oxide, aremono-, di- and triesters of trimethylolpropane or pentaerythritol withlauric acid, coconut fatty acid, tallow fatty acid, palmitic acid,stearic acid, oleic acid, behenic acid and the like.

Anionic emulsifiers. Typical anionic emulsifiers are aliphatic fattyacids with 12 to 22 carbon atoms, such as palmitic acid, stearic acid,or behenic acid, as well as dicarboxylic acids with 12 to 22 carbonatoms such as azelaic acid or sebacic acid.

Amphoteric and cationic emulsifiers. In addition, zwitterionicsurfactants may be used as emulsifiers. Zwitterionic surfactants arethose surface-active compounds which bear at least one quaternaryammonium group and at least one carboxylate and one sulfonate group permolecule. Particularly suitable zwitterionic surfactants are theso-called betaines such as N-alkyl-N,N-dimethylammonium glycinates, forexample cocoalkyl dimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyl dimethylammonium glycinate, and2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines, with in each case8 to 18 carbon atoms in the alkyl or acyl group andcocoacylaminoethylhydroxyethylcarboxymethyl glycinate. Particularlypreferred is the fatty acid amide derivative known by the CTFA namecocamidopropyl betaine. Ampholytic surfactants are also suitableemulsifiers. Ampholytic surfactants are understood to refer to thosesurface-active compounds which, in addition to one C_(8/18)-alkyl oracyl group per molecule, contain at least one free amino group and atleast one —COOH or —SO₃H group and are capable of forming internalsalts. Examples of suitable ampholytic surfactants are N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids with in each case approx. 8 to 18 carbon atoms in the alkyl group.Particularly preferred ampholytic surfactants areN-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate andC_(12/18)-acylsarcosine. Finally, cationic surfactants may also beconsidered as emulsifiers, with those of the esterquat type, preferablymethyl-quaternized difatty acid triethanolamine ester salts, beingparticularly preferred.

Fats and Waxes

Typical examples of fats are glycerides, i.e. solid or liquid vegetableor animal products which consist essentially of mixed glycerol esters ofhigher fatty acids, suitable waxes include natural waxes, for examplecandelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax,guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, montan wax,beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat,ceresin, ozokerite (earth wax), petrolatum, paraffin waxes,microcrystalline waxes; chemically modified waxes (hard waxes), forexample montan ester waxes, sasol waxes, hydrogenated jojoba waxes, andsynthetic waxes, for example polyalkylene waxes and polyethylene glycolwaxes. In addition to the fats, suitable additives are also fat-likesubstances such as lecithins and phospholipids. The term lecithins isunderstood by the person skilled in the art to refer to thoseglycerophospholipids which form from fatty acids, glycerol, phosphoricacid and choline by esterification. Lecithins are thus frequently alsoreferred to as phosphatidylcholines (PC). Examples of natural lecithinswhich may be mentioned are the cephalins, which are also referred to asphosphatidic acids and represent derivatives of1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipidsare usually understood to mean mono- and preferably diesters ofphosphoric acid with glycerol (glycerophosphates), which are generallyconsidered to be fats. In addition, sphingosines and sphingolipids arealso suitable.

Pearlescent Waxes

Examples of suitable pearlescent waxes include: alkylene glycol esters,specifically ethylene glycol distearate; fatty acid alkanolamides,specifically coconut fatty acid diethanolamide; partial glycerides,specifically stearic acid monoglyceride; esters of polyvalent,optionally hydroxy-substituted carboxylic acids with fatty alcoholshaving 6 to 22 carbon atoms, specifically long-chain esters of tartaricacid; fatty substances, for example fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers, and fatty carbonates which have a total of atleast 24 carbon atoms, specifically laurone and distearyl ether; fattyacids, such as stearic acid, hydroxystearic acid or behenic acid,ring-opening products of olefin epoxides having 12 to 22 carbon atomswith fatty alcohols having 12 to 22 carbon atoms and/or polyols having 2to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.

Cooling Agents

Cooling agents are compounds which produce a cool feeling on the skin.As a rule, these are menthol compounds which in addition to the parentsubstance menthol itself are selected for example from the groupcomposed of menthol methyl ether, menthone glyceryl acetal (FEMA GRAS²3807), menthone glyceryl ketal (FEMA GRAS 3808), menthyl lactate (FEMAGRAS 3748), menthol ethylene glycol carbonate (FEMA GRAS 3805), mentholpropylene glycol carbonate (FEMA GRAS 3806), menthyl-N-ethyloxamate,monomethyl succinate (FEMA GRAS 3810), monomenthyl glutamate (FEMA GRAS4006), menthoxy-1,2-propanediol (FEMA GRAS 3784),menthoxy-2-methyl-1,2-propanediol (FEMA GRAS 3849) as ²FEMA [textobscured] defined as “Generally Regarded As Safe” [text obscured]substance is tested according to a standard method and considered to betoxicologically safe. well as the menthane carboxylic acid esters andamides WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30, and mixtures thereof.

A first important representative of these is monomenthyl succinate (FEMAGRAS 3810). Both the succinate and the analog monomenthyl glutarate(FEMA GRAS 4006) are important representatives of monomenthyl estersbased on di- and poly-carboxylic acids:

Examples of applications of these substances can be found for example inthe documents WO 2003 043431 (Unilever) or EP 1332772 A1 (IFF).

The next important group of preferred menthol compounds according to theinvention comprises carbonate esters of menthol and polyols such asglycols, glycerol, or carbohydrates such as menthol ethylene glycolcarbonate (FEMA GRAS 3805=Frescolat® MGC), menthol propylene glycolcarbonate (FEMA GRAS 3784=Frescolat® MPC), menthol2-methyl-1,2-propanediol carbonate (FEMA GRAS 3849), or thecorresponding sugar derivatives. The menthol compounds menthyl lactate(FEMA GRAS 3748=Frescolat® ML), and in particular menthone glycerylacetal (FEMA GRAS 3807) or menthone glyceryl ketal (FEMA GRAS 3808),which is marketed under the brand name Frescolat® MGA, are alsopreferred. Among these substances, menthone glyceryl acetal/ketal,menthyl lactate, and menthol ethylene glycol carbonate or mentholpropylene glycol carbonate, which are marked by the applicant under thenames Frescolat® MGA, Frescolat® ML, Frescolat® MGC, and Frescolat® MPC,have

Menthol compounds, which have a CC bond in the 3 position and also havea number of representatives suitable for use, were first developed inthe 1970s. These are generally referred to as the WS type. The parentsubstance is a menthol derivative in which the hydroxyl group isreplaced by a carboxyl group (WS-1). All other WS types are derived fromthis structure, such as the preferred species WS-3, WS-4, 885-5, 885-12,WS-14 and WS-30.

Bodying Agents and Thickeners

The main suitable bodying agents used are fatty alcohols or hydroxyfatty alcohols containing 12 to 22, and preferably 16 to 18, carbonatoms, as well as partial glycerides, fatty acids or hydroxy fattyacids. A combination of these substances with alkyl oligoglucosidesand/or fatty acid N-methyl glucamides of the same chain length and/orpolyglycerol poly-12-hydroxystearates is preferably used. Suitablethickeners are, for example, Aerosil types (hydrophilic silicas),polysaccharides, in particular xanthan gum, guar-guar, agar-agar,alginates and tyloses, carboxymethylcellulose and hydroxyethyl andhydroxypropyl cellulose, also relatively high molecular weightpolyethylene glycol monoesters and diesters of fatty acids,polyacrylates (for example, Carbopols® and Pemulen types from Goodrich;Synthalensg from Sigma; Keltrol types from Kelco; and Sepigel types fromSeppic; Salcare types from Allied Colloids), polyacrylamides, polymers,polyvinyl alcohol and polyvinyl pyrrolidone. Other bodying agents whichhave proved to be particularly effective are bentonites, for exampleBentone® Gel VS-5PC (Rheox) which is a mixture of cyclopentasiloxane,disteardimonium hectorite, and propylene carbonate. Other suitablebodying agents are surfactants such as ethoxylated fatty acidglycerides, esters of fatty acids with polyols such as pentaerythritolor trimethylol propane, narrow-range fatty alcohol ethoxylates or alkyloligoglucosides, and electrolytes such as sodium chloride and ammoniumchloride.

Superfatting Agents and Stabilizers

As superfatting agents, substances such as lanolin and lecithin, as wellas polyethoxylated or acylated lanolin and lecithin derivatives, polyolfatty acid esters, monoglycerides and fatty acid alkanolamides may beused, with the latter also serving as foam stabilizers.

Metal salts of fatty acids, such as magnesium, aluminum and/or zincstearate or ricinoleate, can be used as stabilizers.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives such as the quaternized hydroxyethyl cellulose obtainablefrom Amerchol under the name Polymer JR 400®, cationic starch,copolymers of diallyl ammonium salts and acrylamides, quaternized vinylpyrrolidone/vinyl imidazole polymers such as Luviquatg (BASF),condensation products of polyglycols and amines, quaternized collagenpolypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen(Lamequat® L, Grünau), quaternized wheat polypeptides,polyethyleneimine, cationic silicone polymers such as amodimethicone,copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine®, Sandoz), copolymers of acrylic acidwith dimethyl diallyl ammonium chloride (Merquatg 550, Chemviron),polyaminopolyamides and crosslinked water-soluble polymers thereof,cationic chitin derivatives such as quaternized chitosan, optionally inmicrocrystalline distribution, condensation products of dihaloalkylenessuch as dibromobutane with bis-dialkylamines, for examplebis-dimethylamino-1,3-propane, cationic guar gum such as Jaguar® CBS,Jaguar® C-17, and Jaguar® C-16 from Celanese, and quaternized ammoniumsalt polymers such as Mirapolg A-15, Mirapol® AD-1, and Mirapol® AZ-1from Miranol.

Examples of suitable anionic, zwitterionic, amphoteric, and nonionicpolymers include vinyl acetate-crotonic acid copolymers, vinylpyrrolidone-vinyl acrylate copolymers, vinyl acetate-butylmaleate-isobornyl acrylate copolymers, methyl vinyl ether-maleicanhydride copolymers and esters thereof, uncrosslinked andpolyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammoniumchloride-acrylate copolymers, octylacrylamide-methylmethacrylate-tert-butylaminoethyl methacrylate-2-hydroxypropylmethacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone-vinylacetate copolymers, vinyl pyrrolidone-dimethylaminoethylmethacrylate-vinyl caprolactam terpolymers, and optionally derivatizedcellulose ethers and silicones.

Silicone Compounds

Examples of suitable silicone compounds are dimethyl polysiloxanes,methylphenyl polysiloxanes, cyclic silicones, and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside-, and/orallyl-modified silicone compounds, which may be both liquid andresin-like at room temperature. Other suitable silicone compounds aresimethicones which are mixtures of dimethicones with an average chainlength of 200 to 300 dimethylsiloxane units and hydrogenated silicates.

UV Protection Factors

UV protection factors are understood for example to be organicsubstances which are liquid or crystalline at room temperature (lightprotection filters) and are capable of absorbing ultraviolet radiationand then releasing the energy absorbed in the form of longer-wavelengthradiation, for example, heat. UV protection factors are usually presentin amounts of 0.1 to 5, and preferably 0.2 to 1 wt %. UV-B filters canbe oil-soluble or water-soluble. The following are examples ofoil-soluble substances:

-   -   3-benzylidene camphor or 3-benzylidene norcamphor and the        derivatives thereof, for example        3-(4-methylbenzylidene)-camphor;    -   4-aminobenzoic acid derivatives, preferably        4-(dimethylamino)benzoic acid-2-ethylhexyl ester,        4-(dimethylamino)benzoic acid-2-octyl ester, and        4-(dimethylamino)benzoic acid amyl ester;    -   cinnamic acid esters, preferably 4-methoxycinnamic        acid-2-ethylhexyl ester, 4-methoxy-cinnamic acid propyl ester,        4-methoxycinnamic acid isoamyl ester, and        2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester        (octocrylene);    -   salicylic acid esters, preferably salicylic acid-2-ethylhexyl        ester, salicylic acid-4-iso-propylbenzyl ester, and salicylic        acid homomenthyl ester;    -   derivatives of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy-4-methoxy-4′-methylbenzophenone, and        2,2′-dihydroxy-4-methoxybenzophenone:    -   benzalmalonic acid esters, preferably 4-methoxybenzalmalonic        acid di-2-ethylhexyl ester;    -   triazine derivatives such as        2,4,6-trianilino-(p-carbo-2′-ethyl-l′-hexyloxy)-1,3,5-triazine        and octyl triazone or dioctyl butamidotriazone (Uvasorb® HEB);    -   propan-1,3-diones such as        1-(4-tert-butylphenyl)-3-(4′methoxyphenyl)propan-1,3-dione; and    -   ketotricyclo(5.2.1.0)decane derivatives.

Suitable water-soluble substances include:

-   -   2-phenylbenzimidazol-5-sulfonic acid and alkali metal, alkaline        earth metal, ammonium, alkylammonium, alkanolammonium, and        glucammonium salts thereof;    -   1H-benzimidazole-4,6-disulfonic acid,        2,2′-(1,4-phenylene)bis-disodium salt (Neo Heliopang AP);    -   sulfonic acid derivatives of benzophenones, preferably        2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts        thereof;    -   sulfonic acid derivatives of 3-benzylidene camphor such as        4-(2-oxo-3-bornylidenemethyl)-benzene sulfonic acid and        2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts        thereof.

Particular examples of typical UV-A filters include derivatives ofbenzoyl methane such as1-(4′-tert-butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione,4-tert-butyl-4′-methoxydibenzoyl methane (Parsol® 1789),2-(4-diethylamino-2-hydroxybenzoyl)-benzoic acid hexyl ester (Uvinulg APlus), 1-phenyl-3-(4′-isopropylphenyl)-propane-1,3-dione, and enaminecompounds. The UV-A and UV-B filters may of course also be used in theform of mixtures. Particularly favorable combinations consist of thederivatives of benzoyl methane, for example4-tert-butyl-4′-methoxydibenzoyl methane (Parsol® 1789) and2-cyano-3,3-phenylcinnamic acid-2-ethyl hexyl ester (octocrylene) incombination with esters of cinnamic acid, preferably 4-methoxycinnamicacid-2-ethyl hexyl ester and/or 4-methoxycinnamic acid propyl esterand/or 4-methoxycinnamic acid isoamyl ester. Such combinations areadvantageously combined with water-soluble filters such as2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earthmetal, ammonium, alkylammonium, alkanolammonium and glucammonium saltsthereof.

In addition to the soluble substances mentioned above, insolublelight-blocking pigments, i.e. finely dispersed metal oxides or salts,may also be used for this purpose. Examples of suitable metal oxidesare, in particular, zinc oxide and titanium dioxide, as well as oxidesof iron, zirconium oxide, silicon, manganese, aluminum and cerium andmixtures thereof. Silicates (talcum), barium sulfate, or zinc stearatemay be used as salts. The oxides and salts are used in the form of thepigments for skin-care and skin-protecting emulsions and decorativecosmetics. The particles should have a mean diameter of less than 100nm, preferably 5 to 50 nm, and more preferably 15 to 30 nm. They may bespherical in shape, but particles having an ellipsoid shape or deviatingin any other way from a spherical shape may also be used. The pigmentsmay also be surface-treated, i.e. hydrophilized or hydrophobized.Typical examples are coated titanium dioxides, for example TitaniumDioxide T 805 (Degussa) and Eusolex® T2000, Eusolex® T, Eusolex® T-ECO,Eusolex® T-S, Eusolex® T-Aqua, Eusolex® T-45D (all from Merck), andUvinul TiO₂ (BASF). Suitable hydrophobic coating materials are above allsilicones, and among these, especially trialkoxyoctylsilanes orsimethicones. So-called micro- or nanopigments are preferably used insun protection products. Micronized zinc oxide such as Z-COTE® or Z-COTEHP1g is preferably used.

Humectants

Humectants are used to further optimize the sensory properties of thecomposition and for moisture regulation of the skin. At the same time,the low-temperature stability of the preparations according to theinvention, in particular in the case of emulsions, is increased.Humectants are ordinarily contained in an amount of 0.1 to 15 wt %,preferably 1 to 10 wt %, and in particular 5 to 10 wt %.

Suitable humectants according to the invention include amino acids,pyrrolidone carboxylic acid, lactic acid and salts thereof, lactitol,urea and urea derivatives, uric acid, glucosamine, creatinine,decomposition products of collagen, chitosan or chitosansalts/derivatives, and in particular polyols and polyol derivatives(e.g. glycerol, diglycerol, triglycerol, ethylene glycol, propyleneglycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethyleneglycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12,PEG-14, PEG-16, PEG-18, and PEG-20), sugar and sugar derivatives (suchas fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol,sorbityl silanediol, sucrose, trehalose, xylose, xylitol, glucuronicacid and salts thereof), ethoxylated sorbitol (sorbeth-6, sorbeth-20,sorbeth-30, sorbeth-40), honey and hydrogenated honey, and hydrogenatedstarch hydrolysate, as well as mixtures of hardened wheat protein andPEG-20 acetate copolymer. According to the invention, particularlysuitable humectants are glycerol, diglycerol, triglycerol, and butyleneglycol.

Biogenic Active Ingredients and Antioxidants

Biogenic active ingredients are understood to refer, for example, totocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid,(deoxy)ribonucleic acid and fragmentation products thereof, β-glucans,retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, aminoacids, ceramides, pseudoceramides, essential oils, plant extracts suchas prune extract and bambaranus extract, and vitamin complexes.

Antioxidants interrupt the photochemical reaction chain triggered whenUV radiation penetrates the skin. Typical examples are amino acids (e.g.glycine, histidine, tyrosine, tryptophan) and the derivatives thereof,imidazole (e.g. urocanic acid) and the derivatives thereof, peptidessuch as D,L-carnosine, D-carnosine, L-carnosine and the derivativesthereof (e.g. anserine), carotenoids, carotenes (e.g. α-carotene,β-carotene, lycopene) and the derivatives thereof, chlorogenic acid andthe derivatives thereof, lipoic acid and the derivatives thereof (suchas dihydrolipoic acid), aurothioglucose, propylthiouracil and otherthiols (such as thioredoxin, glutathione, cysteine, cystine, cystamineand the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl andlauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl, and glyceryl estersthereof) and the salts thereof, dilauryl thiodipropionate, distearylthiodipropionate, thiodipropionic acid and the derivatives thereof(esters, ethers, peptides, lipids, nucleotides, nucleosides and salts)and sulfoximine compounds (such as buthionine sulfoximine, homocysteinesulfoximine, buthionine sulfones, and penta-, hexa-, heptathioninesulfoximine) in very small compatible doses (such as pmol to μmol/kg),also (metal) chelating agents (such as α-hydroxy fatty acids, palmiticacid, phytic acid, lactoferrin), α-hydroxy acids (such as citric acid,lactic acid, malic acid), humic acid, bile acid, bile extracts,bilirubin, biliverdin, EDTA, EGTA and the derivatives thereof,unsaturated fatty acids and the derivatives thereof (such as γ-linolenicacid, linoleic acid, oleic acid), folic acid and the derivativesthereof, ubiquinone and ubiquinol and the derivatives thereof, vitamin Cand derivatives (such as ascorbyl palmitate, Mg ascorbyl phosphate,ascorbyl acetate), tocopherols and derivatives (such as vitamin Eacetate), vitamin A and derivatives (vitamin A palmitate) as well asconiferyl benzoate of benzoic resin, rutinic acid and the derivativesthereof, α-glycosyl rutin, ferulic acid, furfurylidene glucitol,carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacresin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uricacid and the derivatives thereof, mannose and the derivatives thereof,superoxide dismutase, zinc and the derivatives thereof (such as ZnO,ZnSO₄), selenium and the derivatives thereof (such as seleniummethionine), stilbenes and the derivatives thereof (such as stilbeneoxide, trans-stilbene oxide) and derivatives suitable according to theinvention (salts, esters, ethers, sugars, nucleotides, nucleosides,peptides and lipids) of these active ingredients.

Deodorants and Antimicrobial Agents

Cosmetic deodorants (odor inhibitors) counteract, mask, or eliminatebody odors. Body odors result from the action of skin bacteria onapocrine perspiration, causing the formation of decomposition productshaving an unpleasant odor. Accordingly, deodorants contain activeingredients that function as antimicrobial agents, enzyme inhibitors,odor absorbers, or odor-masking agents.

Antimicrobial agents. Suitable antimicrobial agents are, in principle,all substances effective against gram-positive bacteria, for example4-hydroxybenzoic acid and its salts and esters,N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)urea,2,4,4′-trichloro-2′-hydroxydiphenyl ether (triclosan),4-chloro-3,5-dimethylphenol, 2,2′-methylenebis(6-bromo-4-chlorophenol),3-methyl-4-(1-methylethyl)phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-2-propynyl butylcarbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialfragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil,farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate,glycerol monolaurate (GML), diglycerol monocaprate (DMC), and salicylicacid N-alkylamides, for example n-octylsalicylamide orn-decylsalicylamide.

Enzyme inhibitors. Suitable enzyme inhibitors are, for example, esteraseinhibitors. These are preferably trialkyl citrates, such as trimethylcitrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and,in particular, triethyl citrate (Hydagen® CAT). The substances inhibitenzyme activity, thereby reducing odor formation. Other substances whichare suitable esterase inhibitors are sterol sulfates or phosphates, forexample lanosterol, cholesterol, campesterol, stigmasterol andsitosterol sulfate or phosphate, dicarboxylic acids and esters thereof,for example glutaric acid, monoethyl glutarate, diethyl glutarate,adipic acid, monoethyl adipate, diethyl adipate, malonic acid anddiethyl malonate, hydroxycarboxylic acids and esters thereof, forexample citric acid, malic acid, tartaric acid or diethyl tartrate, andzinc glycinate.

Odor absorbers. Suitable as odor absorbers are substances which canabsorb and largely retain odor-forming compounds. They lower the partialpressure of the individual components and thus also reduce their rate ofpropagation. It is important that perfumes remain unaffected thereby.Odor absorbers are not effective against bacteria. They contain as theirmain constituent, for example, a complex zinc salt of ricinoleic acid orspecific, largely odor-neutral fragrances, which are known to the personskilled in the art as “fixatives”, such as extracts of labdanum oil orstyrax oil or certain abietic acid derivatives. Fragrances or perfumeoils, which in addition to their function as odor-masking agents imparttheir respective scent note to deodorants, function as odor-maskingagents. Examples of perfume include mixtures of natural and syntheticfragrances. Natural fragrances are extracts of flowers, stems andleaves, fruits, fruit peels, roots, woods, herbs and grasses, needlesand branches, as well as resins and balsams. Also suitable are animalraw materials, for example civet and castoreum. Typical syntheticfragrance compounds are products of the ester, ether, aldehyde, ketone,alcohol and hydrocarbon type. Fragrance compounds of the ester type are,for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexylpropionate, styrallyl propionate and benzyl salicylate. Theethers include, for example, benzyl ethyl ether, and the aldehydesinclude, for example, the linear alkanals having 8 to 18 carbon atoms,citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde,hydroxycitronellal, lilial and bourgeonal, the ketones include, forexample, the ionones and methyl cedryl ketone, the alcohols includeanethole, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol, and the hydrocarbons include mainlythe terpenes and balsams. Preference is, however, given to usingmixtures of different fragrances which together produce a pleasingfragrance note. Ethereal oils of relatively low volatility, which aremostly used as aroma components, are also suitable as perfume oils, e.g.sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leafoil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, labdanum oil and lavandin oil. Preference is given tousing bergamot oil, dihydromyrcenol, lilial, lyral, citronellol,phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone,cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole,hedione, sandelice, lemon oil, mandarin oil, orange oil, allyl amylglycolate, cyclovertal, lavandin oil, clary sage oil, β-damascone,geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur,iso-E-super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid,geranyl acetate, benzyl acetate, rose oxide, Romilat, Irotyl andFloramat alone or in mixtures.

Antiperspirants. Antiperspirants (perspiration inhibitors) reduce theformation of perspiration by affecting the activity of the eccrine sweatglands, thus counteracting armpit wetness and body odor. Aqueous orwater-free formulations of antiperspirants typically contain thefollowing ingredients:

-   -   astringent active ingredients,    -   oil components,    -   nonionic emulsifiers,    -   coemulsifiers,    -   bodying agents,    -   auxiliaries such as thickeners or complexing agents, and/or    -   nonaqueous solvents such as ethanol, propylene glycol and/or        glycerol.

Suitable astringent antiperspirant active ingredients are primarilysalts of aluminum, zirconium or zinc. Such suitable antihydrotic activeingredients include aluminum chloride, aluminum chlorohydrate, aluminumdichlorohydrate, aluminum sesquichlorohydrate and complex compoundsthereof, e.g. with 1,2-propylene glycol, aluminum hydroxyallantoinate,aluminum chloride tartrate, aluminum zirconium trichlorohydrate,aluminum zirconium tetrachlorohydrate, aluminum zirconiumpentachlorohydrate and complex compounds thereof, e.g. with amino acidssuch as glycine. In addition, customary oil-soluble and water-solubleauxiliaries may be present in antiperspirants in relatively smallamounts. Examples of such oil-soluble auxiliaries are:

-   -   anti-inflammatory, skin-protective, or perfumed ethereal oils,    -   synthetic skin-protective active ingredients, and/or    -   oil-soluble perfume oils.

Common water-soluble additives include preservatives, water-solublefragrances, pH adjusting agents, e.g. buffer mixtures, water-solublethickeners, e.g. water-soluble natural or synthetic polymers such asxanthan gum, hydroxyethylcellulose, polyvinylpyrrolidone, orhigh-molecular polyethylene oxide.

Film-Forming Agents

Common film-forming agents include chitosan, microcrystalline chitosan,quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinylacetate copolymers, polymers of the acrylic acid series, quaternarycellulose derivatives, collagen, hyaluronic acid or salts thereof, andsimilar compounds.

Antidandruff Active Ingredients

Examples of suitable antidandruff active ingredients are piroctoneolamine (1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinonemonoethanolamine salt), Baypival& (climbazole), Ketoconazole®,(4-acetyl-1-{-4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}piperazine,ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfurpolyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate,sulfur tar distillates, salicylic acid (or in combination withhexachlorophene), undecylenic acid monoethanolamide sulfosuccinate Nasalt, Lamepon® UD (protein-undecylenic acid condensate), zincpyrithione, aluminum pyrithione and magnesium pyrithione/dipyrithionemagnesium sulfate.

Swelling Agents

Swelling agents for aqueous phases may be montmorillonites, clayminerals, Pemulen, and alkyl-modified Carbopol grades (Goodrich).Further suitable polymers or swelling agents are given in the overviewby R. Lochhead in Cosm. Toil. 108, 95 (1993).

Insect Repellents

Examples of suitable insect repellents include N,N-diethyl-m-toluamide,1,2-pentanediol, or ethyl butylacetylaminopropionate. A suitableself-tanning agent is dihydroxyacetone. Examples of suitable tyrosineinhibitors, which prevent the formation of melanin and are used indepigmenting agents, include arbutin, ferulic acid, kojic acid, coumaricacid, and ascorbic acid (vitamin C).

Ingredients for Oral and Dental Care Compositions

Oral and dental care compositions are understood to be products used forcleaning and care of the mouth and teeth. Examples are toothpastes,tooth gels, and the like.

Toothpastes or dental creams are generally understood to be gel-like orpasty preparations made from water, thickeners, humectants, abrasive orcleaning agents, surfactants, sweeteners, flavorings, deodorizing activeingredients, as well as active ingredients to combat oral and dentaldiseases. In the toothpastes according to the invention, allcommonly-used cleaning agents, such as chalk, dicalcium phosphate,insoluble sodium metaphosphate, aluminum silicates, calciumpyrophosphate, fine particulate synthetic resins, silicic acids,aluminum oxide, and aluminum oxide trihydrate can be used.

Preferably suitable cleaning agents for the toothpastes according to theinvention are primarily fine particulate silica xerogels, silicahydrogels, precipitated silicas, aluminum oxide trihydrate and fineparticulate a-aluminum oxide or mixtures of these cleaning agents inamounts of 15 to 40 wt % of the toothpaste. Suitable humectants arepredominantly low molecular weight polyethylene glycols, glycerol,sorbitol or mixtures of these products in amounts up to 50 wt %. Amongthe known thickeners, the thickening, fine particulate silica gels andhydrocolloids, such as carboxymethylcellulose, hydroxyethylcellulose,hydroxypropyl guar, hydroxyethyl starch, polyvinylpyrrolidone, highmolecular weight polyethylene glycol, plant gums such as tragacanth,agar agar, carrageenan moss, gum arabic, xanthan gum, and carboxyvinylpolymers (e.g. Carbopol® grades) are suitable. In addition to themixtures of menthofuran and menthol compounds, the oral and dental carecompositions can in particular comprise surface-active substances,preferably anionic and nonionic high-foaming surfactants such as thesubstances already listed above, but in particular alkyl ether sulfatesalts, alkyl polyglucosides, and mixtures thereof.

Further common toothpaste additives are:

-   -   preservatives and antimicrobial substances such as        p-hydroxybenzoic acid methyl, ethyl or propyl ester, sodium        sorbate, sodium benzoate, bromochlorophen, phenylsalicylic acid        esters, thymol and the like;    -   antitartar active ingredients, e.g. organophosphates such as        1-hydroxyethane-1,1-diphosphonic acid,        1-phosphonopropane-1,2,3-tricarboxylic acid, and others, which        are known for example from U.S. Pat. No. 3,488,419, DE 2224430        A1 and DE 2343196 A1;    -   other caries-inhibiting substances such as sodium fluoride,        sodium monofluorophosphate, and stannous fluoride;    -   sweeteners, such as sodium saccharin, sodium cyclamate, sucrose,        lactose, maltose, fructose, or Aspartame®,        (L-aspartyl-L-phenylalanine methyl ester), Stevia extracts, or        sweetening components thereof, in particular ribeaudioside;    -   additional flavoring agents such as eucalyptus oil, anise oil,        fennel oil, cumin oil, methyl acetate, cinnamaldehyde, anethole,        vanillin, and thymol, as well as mixtures of these and other        natural and synthetic flavoring agents;    -   pigments such as titanium dioxide;    -   dyes;    -   buffer substances such as primary, secondary or tertiary alkali        metal phosphates, or citric acid/sodium citrate; and    -   wound-healing and anti-inflammatory substances such as        allantoin, urea, azulene, chamomile active ingredients, and        acetylsalicylic acid derivatives.

A preferred embodiment of the cosmetic preparations is toothpastes inthe form of an aqueous, pasty dispersion comprising polishing agents,humectants, viscosity regulators, and optionally further commoncomponents, as well as the mixture of menthofuran and menthol compoundsin amounts of 0.5 to 2 wt %.

In order to improve flow behavior, hydrotropes such as ethanol,isopropyl alcohol, or polyols can also be used; these substances largelycorrespond to the carriers described above. Polyols that are suitablehere preferably have 2 to 15 carbon atoms and at least two hydroxylgroups. The polyols can also contain further functional groups, inparticular amino groups, or be modified with nitrogen. Typical examplesare

-   -   glycerol;    -   alkylene glycols such as ethylene glycol, diethylene glycol,        propylene glycol, butylene glycol, hexylene glycol, and        polyethylene glycols with an average molecular weight of 100 to        1000 daltons;    -   technical-grade oligoglycerol mixtures with an intrinsic degree        of condensation of 1.5 to 10, such as technical-grade diglycerol        mixtures with a diglycerol content of 40 to 50 wt %;    -   methyol compounds, such as in particular trimethylolethane,        trimethylolpropane, trimethylolbutane, pentaerythritol and        dipentaerythritol;    -   low alkyl glycosides, in particular those having 1 to 8 carbon        atoms in the alkyl radical, such as methyl and butyl glycoside;    -   sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or        mannitol;    -   sugars with 5 to 12 carbon atoms, such as glucose or saccharose;    -   amino sugars, such as glucamine; and    -   dialcohol amines, such as diethanolamine or        2-amino-1,3-propanediol.

Examples of suitable preservatives include phenoxyethanol, formaldehydesolution, parabens, pentanediol or sorbic acid, the silver complexesknown under the name Surfacine®, and the other classes of substancelisted in Annex 6, Part A and B of the Cosmetics Ordinance.

Perfume oils that may be mentioned are mixtures of natural and syntheticfragrances. Natural fragrances are extracts from flowers (lily,lavender, rose, jasmine, neroli, ylang ylang), stems and leaves(geranium, patchouli, petitgrain), fruits (anise, coriander, cumin,juniper), fruit peels (bergamot, lemon, orange), roots (maize, angelica,celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood,guaiac wood, cedar wood, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and branches (spruce, fir, pine,dwarf-pine), and resins and balsams (galbannm, elemi, benzoe, myrrh,olibanum, opoponax). Animal raw materials such as civet and castoreumare also suitable. Typical synthetic fragrance compounds are products ofthe ester, ether, aldehyde, ketone, alcohol and hydrocarbon types.Fragrance compounds of the ester type include benzyl acetate,phenoxyethyl isobutyrate, p-tert-butyl cyclohexyl acetate, linalylacetate, dimethyl benzyl carbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropionate, styrallyl propionate and benzyl salicylate. Theethers include benzyl ethyl ethers, the aldehydes include linearalkanals having 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,lilial and bourgeonal, the ketones include the ionones, α-isomethylionone and methyl cedryl ketone, the alcohols include anethole,citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethylalcohol and terpineol, and the hydrocarbons include primarily theterpenes and balsams. Preferably, however, preference mixtures ofdifferent fragrances which together produce a pleasant scent note areused. Essential oils of lower volatility, which are mostly used asfragrance components, are also suitable as perfume oils, e.g. sage oils,camellia oil, clove oil, melissa oil, mint oil, cinnamon leaf oil,linden blossom oil, juniper berry oil, vetiver oil, olibanum oil,galbanum oil, labolanum oil, and lavandin oil. Preferably, bergamot oil,dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemonoil, mandarin oil, orange oil, allyl amyl glycolate, cyclovertal,lavandin oil, clary sage oil, β-damascone, geranium oil bourbon,cyclohexyl salicylate, Vertofix Coeur, iso-E-Super, Fixolide NP,evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzylacetate, rose oxide, Romilat, Irotyl and Floramat are used alone or inmixtures.

Examples of suitable flavoring agents include peppermint oil, spearmintoil, anise oil, star anise oil, cumin oil, eucalyptus oil, fennel oil,lemon oil, wintergreen oil, clove oil, menthol and the like.

Hydrotropes

In order to improve flow behavior, hydrotropes such as ethanol,isopropyl alcohol, or polyols can be used; these substances largelycorrespond to the carriers specified above. Polyols which are suitablehere preferably have 2 to 15 carbon atoms and at least two hydroxylgroups. The polyols can also contain further functional groups, inparticular amino groups, or be modified with nitrogen. Typical examplesare:

-   -   glycerol;    -   alkylene glycols, such as ethylene glycol, diethylene glycol,        propylene glycol, butylene glycol, hexylene glycol, and        polyethylene glycols with an average molecular weight of 100 to        1000 daltons;    -   technical-grade oligoglycerol mixtures with an intrinsic degree        of condensation of 1.5 to 10 such as technical-grade diglycerol        mixtures with a diglycerol content of 40 to 50 wt %;    -   methylol compounds, such as in particular trimethylolethane,        trimethylolpropane, trimethylol-butane, pentaerythritol, and        dipentaerythritol;    -   lower alkyl glucosides, in particular those with 1 to 8 carbon        atoms in the alkyl radical, such as methyl and butyl glucoside;    -   sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or        mannitol,    -   sugars with 5 to 12 carbon atoms, such as glucose or saccharose;    -   amino sugars such as glucamine; and    -   dialcohol amines, such as diethanolamine or        2-amino-1,3-propanediol.

Preservatives

Examples of suitable preservatives include phenoxyethanol, formaldehydesolution, parabens, pentanediol, or sorbic acid as well as the silvercomplexes known under the name Surfacine® and the other classes ofsubstance listed in Annex 6, Part A and B of the Cosmetics Directive.

Perfume Oils, Flavoring Agents, Flavorings, Fragrances

Preferably, the fragrances and perfume oils used are not subject to anyrestrictions whatsoever. It is therefore possible to use as fragrancesindividual fragrance compounds, either synthetic or natural compounds ofthe class of esters, ethers, aldehydes, ketones, alcohols, hydrocarbons,acids, carbonic esters, aromatic hydrocarbons, aliphatic hydrocarbons,saturated and/or unsaturated hydrocarbons, and mixtures thereof. Thefragrance aldehydes or fragrance ketones used may be all commonfragrance aldehydes and fragrance ketones typically used to produce apleasant fragrance sensation. Suitable fragrance aldehydes and fragranceketones are commonly known to the person skilled in the art. Thefragrance ketones may comprise all ketones which are able to impart adesired fragrance or a sensation of freshness. Mixtures of differentketones may also be used. For example, the ketone may be selected fromthe group consisting of Buccoxime, isojasmone, methyl β-naphthyl ketone,musk indanone, Tonalid/musk plus, α-damascone, β-damascone, δ-damascone,isodamascone, damascenone, damarose, methyl dihydrojasmonate, menthone,carvone, camphor, fenchone, α-ionone, β-ionone, dihydro-p-ionone,γ-methyl so-called ionone, fleuramone, dihydrojasmone, cisjasmone,Iso-E-Super, methyl cedrenyl ketone or methyl cedrylone, acetophenone,methyl acetophenone, para-methoxyacetophenone, methyl β-naphthyl ketone,benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketoneor Livescone, 6-isopropyldecahydro-2-naphthone, dimethyloctenone,Freskomenthe, 4-(1-ethoxyvinyl)-3,3,5,5-tetramethyl cyclohexanone,methyl heptenone,2-(2-(4-methyl-3-cyclohexen-1-yl)propyl)cyclopentanone,1-(p-menthen-6(2)-yl)-1-propanone,4-(4-hydroxy-3-methoxyphenyl)-2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone,4-damascol, dulcinyl or cassione, gelsone, hexalone, isocyclemone E,methyl cyclocitrone, methyl lavender ketone, orivone,para-tert-butylcyclohexanone, verdone, delphone, muscone, neobutenone,plicatone, veloutone, 2,4,4,7-tetramethyloct-6-en-3-one, tetramerane,hedione and mixtures thereof. The ketones may preferably be selectedfrom α-damascone, δ-damascone, isodamascone, carvone, γ-methyl ionone,Iso-E-Super, 2,4,4,7-tetramethyloct-6-en-3-one, benzyl acetone,β-damascone, damascenone, methyl dihydrojasmonate, methyl cedrylone,hedione and mixtures thereof.

Suitable fragrance aldehydes may be any aldehydes that provide a desiredfragrance or feeling of freshness corresponding to the fragranceketones. However, they can also be individual aldehydes or aldehydemixtures. Suitable aldehydes are for example melonal, triplal,ligustral, adoxal, anisaldehyde, cymal, ethyl vanillin, florhydral,floralozone, helional, heliotropin, hydroxycitronellal, koavone, Laurinaldehyde, canthoxal, lyral, lilial, adoxal, anisaldehyde, cumalmethylnonyl acetaldehyde, citronellal, citronellyl oxyacetaldehyde,cyclamene aldehyde, bourgeonal, p,t-bucinal, phenylacetaldehyde,undecylenic aldehyde, vanillin; 2,6,10-trimethyl-9-undecenal,3-dodecen-1-al, α-n-amylcinnamaldehyde, 4-methoxybenzaldehyde,benzaldehyde, 3-(4-tert-butylphenyl)-propanal,2-methyl-3-(para-methoxyphenylpropanal),2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal,3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al,3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxylacetaldehyde,4-isopropylbenzaldehyde,1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,2,4-dimethyl-3-cyclohexene-1-carboxyaldehyde,2-methyl-3-(isopropyl phenyl)propanal, decyl aldehyde,2,6-dimethyl-5-heptenal;4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal;octahydro-4,7-methano-IH-indene carboxaldehyde;3-ethoxy-4-hydroxybenzaldehyde,para-ethyl-α,α-dimethylhydrocinnamaldehyde, α-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,3,4-methylene dioxybenzaldehyde,α-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, α-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyl octanal, undecenal,2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4-(3)(4-methyl-3-pentenyl)-3-cyclohexene carboxaldehyde, 1-dodecanal,2,4-dimethylcyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al,2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal,2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal,3-(4-ethylphenyl)-2,2-dimethylpropanal,3-(4-methoxyphenyl)-2-methylpropanal, methyl nonylacetaldehyde,2-phenylpropan-1-al, 3-phenylprop-2-en-1-al,3-phenyl-2-pentylprop-2-en-1-al, 3-phenyl-2-hexylprop-2-enal,3-(4-isopropyl phenyl)-2-methylpropan-1-al,3-(4-ethylphenyl)-2,2-dimethylpropan-1-al,3-(4-tert-butylphenyl)-2-methyl-propanal,3-(3,4-methylendioxy-phenyl)-2-methylpropan-1-al,3-(4-ethylphenyl)-2,2-dimethylpropanal, 3-(3-isopropylphenyl)-butan-1-al, 2,6-dimethylhept-5-en-1-al, dihydrocinnamaldehyde,1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or 6methoxyhexahydro-4,7-methanoindan-1 or 2-carboxyaldehyde,3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al,4-hydroxy-3-methoxybenzaldehyde,1-methyl-3-(4-methylpentyl)-3-cyclohexene-carboxyaldehyde,7-hydroxy-3,7-dimethyloctanal; trans-4-decenal, 2,6-nonadienal,para-tolylacetaldehyde; 4-methylphenylacetaldehyde,2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal,ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde;5,9-dimethyl-4,8-decadienal, peony aldehyde(6,10-dimethyl-3-oxa-5,9-undecadien-1-al),hexahydro-4,7-methanoindan-1-carboxaldehyde, octanal, 2-methyl octanal,αa-methyl-4-(1-methylethyl)benzene acetaldehyde,6,6-dimethyl-2-norpinene-2-propionaldehyde, paramethylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al,3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde,3-propyl-bicyclo[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal,3-methyl-5-phenyl-1-pentanal, methyl nonyl acetaldehyde,1-p-menthene-q-carboxaldehyde, citral or mixtures thereof, lilialcitral, 1-decanal, n-undecanal, n-dodecanal, florhydral,2,4-dimethyl-3-cyclohexene-1-carboxaldehyde 4-methoxybenzaldehyde,3-methoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde,3,4-methylene dioxybenzaldehyde, and 3,4-dimethoxybenzaldehyde andmixtures thereof. As mentioned in the above examples, the fragrancealdehydes and fragrance ketones can have an aliphatic, cycloaliphatic,aromatic, ethylenically unsaturated structure or a combination of thesestructures. Moreover, there may also be further heteroatoms orpolycyclic structures. The structures can have suitable substituentssuch as hydroxyl or amino groups. For further suitable fragrancesselected from aldehydes and ketones, reference is made to “SteffenArctander, published 1960 and 1969 respectively, reprinted 2000 ISBN:Aroma Chemicals Vol. 1: 0-931710-37-5, Aroma Chemicals Vol. 2:0-931710-38-3”.

Examples of suitable fragrance compounds of the ester type includebenzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexylacetate, linalyl acetate, dimethylbenzyl carbinyl acetate (DMBCA),phenylethyl acetate, benzyl acetate, ethyl methyl phenylglycinate, allylcyclohexyl propionate, styrallyl propionate, benzyl salicylate,cyclohexyl salicylate, floramat, melusat, and jasmacyclate. Examples offragrance compounds of the hydrocarbon type include terpenes such aslimonene and pinene. Examples of suitable fragrances of the ether typeinclude benzyl ethyl ether and ambroxan. Examples of suitable fragrancealcohols include 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methyl pentanol, 2-phenoxyethanol, 2-phenyl propanol,2-tert-butyl cyclohexanol, 3,5,5-trimethyl cyclohexanol, 3-hexanol,3-methyl-5-phenyl pentanol, 3-octanol, 1-octen-3-ol, 3-phenyl propanol,4-heptenol, 4-isopropyl cyclohexanol, 4-tert-butyl cyclohexanol,6,8-dimethyl-2-nonanol, 6-nonan-1-ol, 9-decen-1-ol, a-methylbenzylalcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzylsalicylate, β-terpineol, butyl salicylate, citronellol, cyclohexylsalicylate, decanol, dihydromyrcenol, dimethylbenzyl carbinol, dimethylheptanol, dimethyl octanol, ethyl salicylate, ethylvanilin, anethol,eugenol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol,isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol,octanol, para-menthan-7-ol, phenylethyl alcohol, phenol, phenylsalicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol,trans-2-cis-6-nonadienol, trans-2-nonen-1-ol, trans-2-octenol,undecanol, vanillin, and cinnamyl alcohol, and if a plurality offragrance alcohols are present, they may be selected independently ofone another.

Fragrances or perfume oils can also be natural fragrance mixtures, suchas those obtainable from plant sources, e.g. pine, citrus, jasmine,patchouli, rose or ylang-ylang oil. Also suitable are clary sage oil,camomile oil, clove oil, balm oil, mint oil, cinnamon leaf oil, limeblossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oiland labdanum oil, and also orange blossom oil, neroli oil, orange peeloil and sandalwood oil. Essential oils such as angelica root oil,aniseed oil, arnica blossom oil, basil oil, bay oil, champaca floweroil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil,fennel oil, pine needle oil, galbanum oil, geranium oil, gingergrassoil, guaiac wood oil, gurjan balsam oil, helichrysum oil, ho oil, gingeroil, iris oil, cajeput oil, sweet flag oil, camomile oil, camphor oil,cananga oil, cardamom oil, cassia oil, pine needle oil, copaiba balsamoil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil,lemongrass oil, lime oil, mandarin oil, melissa oil, amber seed oil,myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, oreganooil, palmarosa oil, patchouli oil, peru balsam oil, petitgrain oil,pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemaryoil, sandalwood oil, celery oil, spike oil, star anise oil, turpentineoil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil,wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamonoil, cinnamon leaf oil, citronella oil, citrus oil, and cypress oil.

So-called fragrance precursors (pro-drugs) are also suitable as fragrantsubstances. This class of compounds comprises compounds which release adesired odor molecule and/or fragrance molecule through the breaking ofa chemical bond, by hydrolysis, for example. In order to form afragrance precursor, a desired fragrance raw material is typicallyjoined chemically to a carrier, preferably a carrier of low or moderatevolatility. The combination results in a less volatile and more stronglyhydrophobic fragrance precursor, with better attachment to materials.The fragrance is released subsequently by breaking of the bond betweenthe fragrance raw material and the carrier, as a result of the change inpH, for example (through perspiration during wear, for example),atmospheric humidity, heat and/or sunlight during storage or drying on aclothesline.

The fragrance raw material for use in fragrance precursors typicallycomprises saturated or unsaturated volatile compounds containing analcohol, an aldehyde and/or a ketone group. The fragrance raw materialsthat are useful herein include any pleasingly fragrant substances ormixtures of substances which have already been described above.

Particularly advantageous fragrance precursors which can be used conformto Formula (III)

R—C(OR¹)(OR²)—OR³   (III)

where R denotes hydrogen, linear C₁-C₈ alkyl, branched C₃-C₂₀ alkyl,cyclic C₃-C₂₀ alkyl, branched cyclic C₆-C₂₀ alkyl, linear C₆-C₂₀alkenyl, branched C₆-C₂₀ alkenyl, cyclic C₆-C₂₀ alkenyl, branched cyclicC₆-C₂₀ alkenyl, substituted or unsubstituted C₆-C₂₀ aryl and mixturesthereof; R¹, R² and R³ independently are linear, branched, orsubstituted C₁-C₂₀ alkyl; linear, branched or substituted C₂-C₂₀alkenyl; substituted or unsubstituted cyclic C₃-C₂₀ alkyl; substitutedor substituted C₆-C₂₀ aryl, substituted or unsubstituted C₂-C₄₀alkyleneoxy; substituted or unsubstituted C3-C₄₀ alkylene oxyalkyl;substituted or unsubstituted C₆-C₄₀ alkylene aryl; substituted orunsubstituted C6-C₃₂ aryloxy; substituted or unsubstituted C₆-C₄₀alkylene oxyaryl; C₆-C₄₀ oxyalkylenearyl and mixtures thereof. The useof such substances, in particular in (preferably water-insoluble)microcapsules, corresponds to a preferred embodiment of the invention.

Further particularly preferred fragrance precursors are acetals orketals, preferably of Formula (IV):

R—O(R¹)(OR³)—OR²   (IV)

where R denotes a linear C₁-C₂₀ alkyl, branched C₃-C₂₀ acyl, cyclicC₆-C₂₀ alkyl, branched cyclic C₆-C₂₀ alkyl, linear C₆-C₂₀ alkenyl,branched C₃-C₂₀ alkenyl, cyclic C₆-C₂₀ alkenyl, branched cyclic C₆-C₂₀alkenyl, substituted or unsubstituted C₆-C₂₀ aryl, and mixtures thereof;R¹ is hydrogen or R; R² and R³, each independently of one another, areselected from the group composed of linear C₁-C₂₀ alkyl, branched C₃-C₂₀alkyl, cyclic C₃-C₂₀ alkyl, branched cyclic C₆-C₂₀ alkyl, linear C₆-C₂₀alkenyl, branched C₆-C₂₀ alkenyl, cyclic C₆-C₂₀ alkenyl, branched cyclicC₆-C₂₀ alkenyl, C₆-C₂₀ aryl, substituted C₇-C₂₀ aryl, and mixturesthereof. The use of such substances, in particular in (preferablywater-insoluble) microcapsules, corresponds to a preferred embodiment ofthe invention.

Further particularly advantageous fragrance precursors suitable for useconform to Formula (V)

R⁴OC(OR¹)(OR³)—OR²   (V)

where R¹, R², R³ and R⁴, independently of one another, are linear,branched or substituted C₁-C₂₀ alkyl; linear, branched or substitutedC₂-C₂₀ alkenyl; substituted or unsubstituted cyclic C₅-C₂₀ alkyl;substituted or unsubstituted C₆-C₂₀ aryl, substituted or unsubstitutedC₂-C₄₀ alkyleneoxy; substituted or unsubstituted C₃-C₄₀ alkyleneoxyalkyl; substituted or unsubstituted C₆-C₄₀ alkylene aryl; substitutedor unsubstituted C₆-C₃₂ aryloxy; substituted or unsubstituted C₆-C₄₀alkylene oxyaryl; C₆-C₄₀ oxyalkylene aryl; and mixtures thereof. The useof such substances, in particular in (preferably water-insoluble)microcapsules, corresponds to a preferred embodiment of the invention.

It is particularly preferable if the fragrances used comprise silicicacid ester mixtures. Silicic acid esters are described, for example, byFormula (V)

R—(—O—Si(OR)₂—)_(n)—OR   (V)

where each R is independently selected from the group containing H,linear or branched, saturated or unsaturated, substituted orunsubstituted C₁-C₆ hydrocarbon radicals and fragrance alcohol radicalsand/or biocide alcohol radicals, m adopts values from the range of 1 to20, and n adopts values from the range of 2 to 100. Preferably, thesilicic esters of the formulae contain at least one fragrance alcoholradical and/or biocide alcohol radical.

The silicic acid ester mixtures can be used in encapsulated, but alsounencapsulated, form. The presence of silicic acid ester mixtures oftenmakes it possible to even further improve the fragrance impressionobtainable, with respect to both pleasant aroma and intensity. Thefragrance impression is not only better from a qualitative standpoint,i.e. with respect to pleasant aroma, but is also longer-lasting.

The silicic acid ester mixtures can also be contained in themicrocapsules. If the silicic acid ester mixtures in the microcapsulespreferably account for at least 2 wt % of the total amount ofencapsulated fragrances, i.e. in wt % relative to the amount ofencapsulated fragrances, this constitutes a preferred embodiment of theinvention, which provides a further improvement in the desired fragranceeffect after drying.

Particularly suitable fragrance precursors are reaction products ofcompounds comprising at least one primary and/or secondary amine group,for example an aminofunctional polymer, in particular an aminofunctionalsilicone, and a fragrance component selected from a ketone, an aldehyde,and mixtures thereof. Suitable flavoring agents are, for example,peppermint oil, spearmint oil, anise oil, star anise oil, cumin oil,eucalyptus oil, fennel oil, lemon oil, wintergreen oil, clove oil,menthol and the like.

Examples of flavorings include: acetophenone, allyl caproate, α-ionone,β-ione, anisaldehyde, anisyl acetate, anisyl formate, benzaldehyde,benzothiazole, benzyl acetate, benzyl alcohol, benzyl benzoate,β-ionone, butyl butyrate, butyl caproate, butylidene phthalide, carvone,camphene, caryophyllene, cineol, cinnamyl acetate, citral, citronellol,citronellal, citronellyl acetate, cyclohexyl acetate, cymene, damascone,decalactone, dihydrocoumarin, dimethyl anthranilate, dimethylanthranilate, dodecalactone, ethoxyethyl acetate, ethylbutyric acid,ethyl butyrate, ethyl caprinate, ethyl caproate, ethyl crotonate, ethylfuraneol, ethyl guaiacol, ethyl isobutyrate, ethyl isovalerate, ethyllactate, ethyl methyl butyrate, ethyl propionate, eucalyptol, eugenol,ethyl heptylate, 4-(p-hydroxyphenyl)-2-butanone, γ-decalactone,geraniol, geranyl acetate, geranyl acetate, grapefruit aldehyde, methyldihydrojasmonate (e.g. Hedion®, heliotropin, 2-heptanone, 3-heptanone,4-heptanone, trans-2-heptenal, cis-4-heptenal, trans-2-hexenal,cis-3-hexenol, trans-2-hexenoic acid, trans-3-hexenoic acid,cis-2-hexenyl acetate, cis-3-hexenyl acetate, cis-3-hexenyl caproate,trans-2-hexenyl caproate, cis-3-hexenylformate, cis-2-hexyl acetate,cis-3-hexyl acetate, trans-2-hexyl acetate, cis-3-hexylformate,para-hydroxybenzyl acetone, isoamyl alcohol, isoamyl isovalerate,isobutyl butyrate, isobutyraldehyde, isoeugenol methyl ether, isopropylmethylthiazole, lauric acid, levulinic acid, linalool, linalool oxide,linalyl acetate, menthol, menthofuran, methyl anthranilate, methylbutanol, methyl butyric acid, 2-methylbutyl acetate, methyl caproate,methyl cinnamate, 5-methyl furfural, 3,2,2-methyl cyclopentenolone,6,5,2-methyl heptenone, methyl dihydrojasmonate, methyl jasmonate,methyl 2-methyl butyrate, 2-methyl-2-pentenolic acid, methylthiobutyrate, 3,1-methyl thiohexanol, 3-methyl thiohexyl acetate, nerol,neryl acetate, trans,trans-2,4-nonadienal, 2,4-nonadienol,2,6-nonadienol, 2,4-nonadienol, nootkatone, δ-octalactone, gammaoctalactone, 2-octanol, 3-octanol, 1,3-octenol, 1-octyl acetate, 3-octylacetate, palmitic acid, paraldehyde, phellandrene, pentanedione,phenylethyl acetate, phenylethyl alcohol, phenylethyl alcohol,phenylethyl isovalerate, piperonal, propionaldehyde, propyl butyrate,pulegon, pulegol, sinensal, sulfurol, terpinene, terpineol, terpinolene,8,3-thiomenthanone, 4,4,2-thiomethyl pentanone, thymol, δ-undecalactone,γ-undecalactone, valencene, valeric acid, vanillin, acetoin,ethylvanillin, ethylvanillin isobutyrate (=3-ethoxy-4-isobutyryloxybenzaldehyde), 2,5-dimethyl-4-hydroxy-3(2H)-furanone and thederivatives thereof (and preferably homofuraneol(=2-ethyl-4-hydroxy-5-methyl-3(2H)-furanone), homofuronol(=2-ethyl-5-methyl-4-hydroxy-3(2H)-furanone, and5-ethyl-2-methyl-4-hydroxy-3(2H)-furanone), maltol and maltolderivatives (preferably ethyl maltol), coumarin and coumarinderivatives, γ-lactones (and preferably γ-undecalactone, γ-nonalactone,γ-decalactone), δ-lactones (preferably 4-methyl δ-decalactone, massoialactone, δ-decalactone, and tuberolactone), methyl sorbate, divanillin,4-hydroxy-2(or 5)-ethyl-5(or 2)-methyl-3(2H)furanone,2-hydroxy-3-methyl-2-cyclopentenone,3-hydroxy-4,5-dimethyl-2(5H)-furanone, acetic acid isoamyl ester,butyric acid ethyl ester, butyric acid-n-butyl ester, butyric acidisoamyl ester, 3-methyl-butyric acid ethyl ester, n-hexanoic acid ethylester, n-hexanoic acid allyl ester, n-hexanoic acid-n-butyl ester,n-octanoic acid ethyl ester, ethyl-3-methyl-3-phenylglycidate,ethyl-2-trans-4-cis-decadienoate, 4-(p-hydroxyphenyl)-2-butanone,1,1-dimethoxy-2,2,5-trimethyl-4-hexane, 2,6-dimethyl-5-hepten-1-al andphenylacetaldehyde, 2-methyl-3-(methylthio)furan, 2-methyl-3-furanthiol,bis(2-methyl-3-furyl)disulfide, furfuryl mercaptan, methional,2-acetyl-2-thiazoline, 3-mercapto-2-pentanone,2,5-dimethyl-3-furanthiol, 2,4,5-trimethyl thiazole, 2-acetylthiazole,2,4-dimethyl-5-ethylthiazole, 2-acetyl-1-pyrroline, 2-methyl-3-ethylpyrazine, 2-ethyl-3,5-dimethyl pyrazine, 2-ethyl-3, 6-dimethyl pyrazine,2,3-diethyl-5-methyl pyrazine, 3-isopropyl-2-methoxypyrazine,3-isobutyl-2-methoxypyrazine, 2-acetylpyrazine, 2-pentylpyridine,(E,E)-2,4-decadienal, (E,E)-2,4-nonadienal, (E)-2-octenal,(E)-2-nonenal, 2-undecenal, 12-methyl tridecanal, 1-penten-3-one,4-hydroxy-2,5-dimethyl-3(2H)-furanone, guaiacol,3-hydroxy-4,5-dimethyl-2(5H)-furanone,3-hydroxy-4-methyl-5-ethyl-2(5H)-furanone, cinnamaldehyde, cinnamylalcohol, methyl salicylate, isopulegol and (not explicitly stated here)stereoisomers, enantiomers, positional isomers, diastereomers,cis/trans-isomers, or epimers of these substances.

Preferably, mixtures of various fragrances (from the various fragranceclasses mentioned above) are used which combine to produce an attractivescent note. In this case, the total amount of the at least one fragranceis the amount of all of the fragrances in the mixture together relativeto the total amount of the agent.

Dyes

Substances that are suitable and approved for cosmetic purposes can beused as dyes, such as those listed in the publication “Cosmetic ColoringAgents” of the Colorant Commission of the German Research Foundation,Verlag Chemie, Weinheim, 1984, pp. 81-106. Examples include CochinealRed A (C.I. 16255), Patent Blue V (C.I. 42051), indigotin (C.I. 73015),chlorophyllin (C.I. 75810), Quinoline Yellow (C.I. 47005), titaniumdioxide (C.I. 77891), Indanthrene Blue RS (C.I. 69800) and madder lake(C.I.58000). Luminol can also be included as a luminescent dye. Thesedyes are ordinarily used in concentrations of 0.001 to 0.1 wt %,relative to the total mixture.

The total amount of the auxiliary substances and additives can be 1 to50, and preferably 5 to 40 wt % relative to the dyes. The production ofthe dyes can be carried out by common cold or hot processes; the phaseinversion temperature method is preferred.

The following known approved food dyes are also suitable:

Allurarot AC E 129 red Aluminum E 173 silver-grey Amaranth E 123 redAnthocyanins E 163 violet, blue Azorubin E 122 red Betanin E 162 redBrown FK E 154 yellowish-brown Brown HT E 155 reddish-brown BrilliantBlue FCF E 133 blue Brilliant Black BN E 151 violet, brown, blackCalcium carbonate E 170 Canthaxanthin E 161 g Carotene E 160 a Annatto(Norbixin) E 160 b Capsanthin E 160 c Lycopene E 160 d8′-β-apo-8′-carotenal E 160 e Ethyl 8′-apo-β- E 160 f caroten-8′-oateQuinoline Yellow E 104 Chlorophyll E 140 green Cochineal Red A E 124Curcumin E 100 Iron oxide E 172 Erythrosine E 127 Orange Yellow S E 110Gold E 175 Green S E 142 Indigotin E 132 Cochineal E 120Copper-containing E 141 complexes of chlorophylls and chlorophyllinsLactoflavin E 101 Lithol Rubine BK E 180 Lutein E 161 b Patent Blue V E131 Vegetable carbon E 153 Riboflavin (vitamin E 101 B2) Riboflavin5-phosphate E 101 a Safflower cherry red to brownish-yellow Silver E 174Tartrazine E 102 lemon yellow Titanium dioxide E 171 Caramel E 150 aCaustic sulfite E 150 b caramel Ammonia caramel E 150 c Ammonia sulfiteE 150 d caramel Zeaxanthin E 161 h

Dyes are to be distinguished from coloring food products, which can alsobe used here. In contrast to the dyes, whose exact composition isprescribed by law and have been evaluated for safety by regulatoryagencies with respect to their effects on human health, extracts fromfoods that have a coloring effect are being increasingly used. Examplesinclude spinach extract (green noodles, pistachio ice cream), red beetextract, and curcumin extract.

INDUSTRIAL APPLICABILITY

The capsules according to the invention can be used in virtually anyarea, particularly in areas in which active ingredients and activeingredient substances are to be stabilized in order to incorporate theminto a composition, so that they can later be released in a controlledmanner over a specified period of time.

The capsules according to the invention are particularly suitable forincorporating active ingredients and active substances into cosmeticproducts or pharmaceutical agents and stabilizing them. In particular,they are used in the production of pharmaceutical agents or cosmeticproducts for use on the skin or oral use.

The capsules according to the invention are advantageous in that theycan have a high content and may enclose any type of active ingredientsand active substances. In particular, the capsules according to theinvention are usable in the area of food products, because they aretoxicologically safe.

EXAMPLES Example 1 Production of Alginate Based Capsules

Alginate and gum arabic are fully dissolved in an amount of water heatedto 40° C. while stirring. Wheat fibers are added to this mixture inhomogeneous distribution. If coloring is desired, the dye is firstdissolved in the flavoring agent. The flavoring agent is then added tothe previously produced mixture and homogeneously dispersed (UltraTurrax® or homogenizer). The mixture is added dropwise to a calciumhardening bath adjusted to a temperature of 7-10° C. The resultingcapsules are sieved off, washed, and dried in the fluidized bed.

Both alginate and pectin based capsules were produced as described abovein which an active ingredient (e.g. a flavoring agent) was encapsulated.

In one case, an amidated pectin was used that could be applied exactlylike the alginate in comparable formulations.

Moreover, mixtures of low-esterified pectins (e.g. citrus pectin, applepectin, other low-esterified pectins) with alginates were tested, with aratio of alginate to pectin in the range of 1:2 to 2:1.

Moreover, alginate-gellan based capsules were produced as specifiedabove, with the range of ratio of alginate to gellan being in the rangeof 3:2 to 3:1.

TABLE 1 Alginate-gellan gum based capsules Components K1 wt % K2 wt % K3wt % K4 wt % Alginate 1.03 1.18 — 0.68 Pectin — — 1.33 0.65 Gum arabic0.65 0.74 0.83 0.83 Wheat fibers 0.56 0.64 0.77 0.77 Flavoring agent6.89 7.88 8.82 8.82 Colorant 0.02 0.02 0.02 0.02 Gellan gum 0.37 0.84 —— Water Add to Add to Add to Add to 100 100 100 100 Content Approx.Approx. Approx. Approx. 75% 75% 75% 75%

The resulting alginate-gellan gum capsules show an average size of 925to 955, with use of a 0.5 mm nozzle, temp. dispersion of 40° C., temp.cal. bath 10-15° C., pressure dispersion of 0.19 bar, frequency of 250Hz, amplitude of 0.75 A, temp. hardening bath 7-10° C., flow rate 0.8kg/h, drying with silicon diox. 103846 approx. 10%, and Aeromatic dryingat 45° C. for approx. 35 min to 45 min.

The ratios of the components in the standard formulation of a gel beadbefore and after drying are as follows for alginate capsules:

TABLE 3 Ratio of individual components in an alginate capsule Beforedrying After drying Components wt % wt % Water 88.231 — Flavoring agent8.823 75.11 Sodium alginate E401 1.325 11.28 high viscous Gum arabictype SEYAL 0.827 7.00 Wheat fibers WF 600-30 0.772 6.57

Example 2 Production of an O/W Emulsion

Mixtures A and B were separately heated to 80° C., and mixture B wasthen dispersed in mixture A. Mixture C was then added to mixture AB andemulsified using an Ultra Turrax Stirrer (3 min). After this, theemulsion was neutralized with D and cooled. The capsules according tothe invention (E) were incorporated into emulsions E1 and E2 and couldthus be tested.

TABLE 2 O/W emulsions into which the capsules according to the inventionare incorporated Raw material INCI E1 w/w % E2 w/w % A. EmulsiphosPotassium Cetyl 2.0 2.0 Phosphate, Hydrogenated Palm Glycerides CutinaPES Pentaerythrityl 2.0 2.0 Distearate PCL Solid Stearyl Heptanoate, 2.02.0 Stearyl Caprylate Lanette O Cetearyl Alcohol 2.5 2.5 PCL Liquid 100Cetearyl 5.0 5.0 Ethylhexanoate Isodragol Triisononanoin 2.0 2.0 DowCorning 246 Cyclohexasiloxane, 2.0 2.0 Fluid Cyclopentasiloxane Dragoxat89 Ethylhexyl 3.0 3.0 Isononanoate B. Ultrez-10 Carbomer 0.2 0.2 KeltrolCG Xanthan Gum 0.15 0.15 C. Wasser Water (Aqua) 71.05 71.15 EDTA BDDisodium EDTA 0.1 — Hydrolite-5 Pentylene Glycol 2.0 2.0 PropyleneGlycol Propylene Glycol 2.0 2.0 SymDiol 68 1,2 Hexanediol, 0.6 0.6Caprylyl Glycol Glycerin 85% Glycerin 2.0 2.0 D. Sodium Hydroxide SodiumHydroxide 0.4 0.4 10% sol. E. Capsules K2 (75% active) 1.0 1.0 accordingto the invention

Example 3 Storage Tests

The emulsions of example 2, which the capsules according to theinvention contain, were stored at various temperatures and visually andmicroscopically examined.

TABLE 3 Storage test results T = 5° C. T = RT T = 40° C. Emulsion 3months 2 days 3 months 1 week 2 weeks 3 months E1 — All capsules — — — —decomposed E2 Stable Stable Stable Stable Stable Capsules slightlyswollen, but still recognizable as particles

Emulsion 1 with EDTA no longer showed any capsules after 2 days at RT.After 2 days, all capsules were destroyed and dissolved in the emulsion.Emulsion 2 showed better stability at various storage temperatures. Evenafter 3 months, capsules were still visible and microscopicallydetectable in the emulsion, although the capsules were slightly swollenafter 3 months of storage. When the emulsion was rubbed onto the skin,the capsules disintegrated and released the active ingredient.

Example 4 Storage Tests in Products

The dried capsules according to the invention were incorporated intotoothpaste, margarine and skin cream and stored after 3 months at roomtemperature.

The dried capsules were stable after 3 months and showed no changeswhatsoever. As for the capsules that had been incorporated intotoothpaste, the alginate or pectin based capsules were highly swollen,but the capsule structure remained recognizable. The capsules based onalginate-gellan gum showed improved stability. These capsules were stillstable after 1 month of storage at RT.

In the margarine and the skin cream, the capsules remained stable evenafter 3 months.

Example 5 Formulation Examples A to G Chewing Gum Pastes A-C

The capsules according to the invention were incorporated into chewinggum pastes as shown in Table 4.

TABLE 4 Chewing gum pastes A-C Composition A B C Polyisobutylene (MW20,000) 20.0 25.0 30.0 Sorbitol 51.0 47.5 44.5 Mannitol 5.0 4.3 3.6Glycerol 8.0 8.0 7.0 Lycasin:glycerol (1:1) 8.2 8.0 7.0 Lecithin 0.2 0.20.2 Flavoring mixture 1.0 1.0 1.0 Water to 100

Cosmetic Compositions D-G Containing Capsules According to the Invention

In D and E, flavoring agents were incorporated into the capsulesaccording to the invention.

In creams F and G, cooling agents were incorporated into the capsulesaccording to the invention.

D=bath lotion, E=soft cream, F, G=moisturizing cream

TABLE 5 Example formulations D-G of a cosmetic preparation Components(INCI) D E F G Texapon ® NSO — — — — Sodium Laureth Sulfate Plantacare ®818 — — — — Coco Glucosides Plantacare ® PS 10 22.0 — — — Sodium LaurethSulfate (and) Coco Glucosides Dehytong PK 45 15.0 — — — CocamidopropylBetaine Emulgade ® SE — 5.0 5.0 4.0 Glyceryl Sterate (and) Ceteareth12/20 (and) Cetearyl Alcohol (and) Cetyl Palmitate Eumulgin ® B1 — — —1.0 Ceteareth-12 Lameform ® TGI — — — — Polyglyceryl-3 IsostearateDehymuls ® PGPH — — — — Polyglyceryl-2 Dipolyhydroxystearate Monomuls ®90-O 18 — — — — Glyceryl Oleate Cetiol ® HE 2.0 — — — PEG-7 GlycerylCocoate Cetiol ® OE — — — — Dicaprylyl Ether Cetiol ® PGL — — — 3.0Hexyldecanol (and) Hexyldecyl Laurate Cetiol ® SN 1.0 3.0 3.0 — CetearylIsononanoate Cetiol ® V — 3.0 3.0 — Decyl Oleate Myritol ® 318 — — — 3.0Coco Caprylate Caprate Bees Wax — — — — Nutrilan ® Elastin E20 — 2.0 — —Hydrolyzed Elastin Nutrilan ® I-50 — — 2.0 — Hydrolyzed CollagenGluadin ® AGP 0.5 — — 0.5 Hydrolyzed Wheat Gluten Gluadin ® WK 2.0 — — —Sodium Cocoyl Hydrolyzed Wheat Protein Euperlan ® PK 3000 AM 5.0 — — —Glycol Distearate (and) Laureth-4 (and) Cocamidopropyl Betaine Arylpon ®F Laureth-2 Hydagen ® CHF 1.0 1.0 1.0 1.0 Chitosan Capsules according tothe invention 1.0 1.0 1.0 1.0 Glycerol (86 wt. %) — 3.0 3.0 5.0 Wateradd to 100 100 100 100

1. A capsule, comprising (a) at least one gelable substance, (b) atleast one emulsifier, (c) at least one filler and (d) at least oneactive ingredient or active substance which is to be encapsulated, withthe active ingredient or active substance (d) being dispersed in anemulsion comprising the gelable substance (a), the emulsifier (b) andthe filler (c).
 2. The capsule as claimed in claim 1, wherein thegelable substance (a) is selected from the group consisting composed ofalginate, pectin, agar-agar, carrageenan, gellan gum, gelatins, modifiedcellulose, proteins and mixtures thereof, the emulsifier (b) is selectedfrom the group consisting of polysorbates, sugar esters, saponins, gumarabic, modified gum Arabic, modified starch and mixtures thereof, andthe filler (c) is selected from the group consisting of vegetablefibers, microcrystalline cellulose, silica gels, native starch,silicates and mixtures thereof.
 3. The capsule as claimed in claim 1,wherein the gelable substance is selected from the group consisting ofalginate, pectin, gellan gum and mixtures thereof.
 4. The capsule asclaimed in claim 1, wherein the filler is a vegetable fiber which isselected from the group consisting of apple fibers, bamboo fibers, oatfibers, pea fibers, potato fibers, wheat fibers and mixtures thereof. 5.The capsule as claimed in claim 1, wherein the emulsifier is selectedfrom the group consisting of gum arabic, modified gum arabic, modifiedstarch and mixtures thereof.
 6. The capsule as claimed in claim 1,wherein the active ingredient or the active substance is selected fromthe group consisting of flavorings, fragrances, dietary supplements suchas vitamins, minerals, antioxidants, anthocyanins and coenzyme 10,cosmetic active substances, pharmaceutically active substances andmixtures thereof.
 7. The capsule as claimed in claim 1, wherein theratio of the emulsifier to the filler is in the range of 2:1 to 1:2. 8.The capsule as claimed in claim 1, wherein the active ingredient contentof the capsules is between 20 and 95 wt %.
 9. The capsule as claimed inclaim 1, wherein the capsules have a mean average diameter of 200 to1500 μm.
 10. A cosmetic product, pharmaceutical composition, food orbeverage comprising the capsule as claimed in claim
 1. 11. A method forthe production of the capsule as claimed in claim 1, comprising (i)formation of a mixture of a) at least one gelable substance, b) at leastone emulsifier, c) at least one filler, and d) at least one activeingredient or active substance, (ii) addition of drops of the mixture ofi) to a solution of a multivalent cation, so that crosslinking occursand gelation takes place, (iii) separation of the capsule formed fromstep ii), and (iv) drying of the capsule obtained from step iv).
 12. Amethod for preparing a cosmetic product, pharmaceutical composition,food or beverage comprising adding the capsule as claimed in claim 1 tothe cosmetic product, pharmaceutical composition, food or beverage. 13.A method for preparing a pharmaceutical composition or cosmetic productfor use on skin or orally, comprising adding the capsule as claimed inclaim 1 to the pharmaceutical composition or cosmetic product for use onthe skin or for oral use.
 14. A method for the controlled, prolonged,delayed delivery and release of an active ingredient or activesubstance, comprising adding the capsule as claimed in claim 1 to acosmetic product, pharmaceutical composition, food or beverage.
 15. Amethod for preparing a capsule, comprising: (i) formation of a mixtureof (a) at least one gelable substance, (b) at least one emulsifier, (c)at least one filler, and d) at least one active ingredient or activesubstance, (ii) addition of drops of the mixture of i) to a solution ofa multivalent cation, so that crosslinking occurs and gelation takesplace, (iii) separation of the capsule formed from step ii), and (iv)drying of the capsule obtained from step iv), wherein the gelablesubstance (a) is selected from the group consisting of alginate, pectin,agar-agar, carrageenan, gellan gum, gelatins, modified cellulose,proteins and mixtures thereof, the emulsifier (b) is selected from thegroup consisting of polysorbates, sugar esters, saponins, gum arabic,modified starch and mixtures thereof, and the filler (c) is selectedfrom the group consisitng of vegetable fibers, microcrystallinecellulose, silica gels, native starches, silicates and mixtures thereof.